CN106575078A - Photosensitive composition, method for producing curable film, curable film, touch panel, touch panel display device, liquid crystal display device, and organic el display device - Google Patents

Photosensitive composition, method for producing curable film, curable film, touch panel, touch panel display device, liquid crystal display device, and organic el display device Download PDF

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Publication number
CN106575078A
CN106575078A CN201580038645.7A CN201580038645A CN106575078A CN 106575078 A CN106575078 A CN 106575078A CN 201580038645 A CN201580038645 A CN 201580038645A CN 106575078 A CN106575078 A CN 106575078A
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Prior art keywords
composition
mass
photosensitive composite
compound
methyl
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Granted
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CN201580038645.7A
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CN106575078B (en
Inventor
米泽裕之
崎田享平
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0412—Digitisers structurally integrated in a display
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Human Computer Interaction (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The purpose of the present invention is to provide a photosensitive composition capable of obtaining a curable film exhibiting excellent reliability even when heated to a low-temperature, and also capable of photolithographic patterning. This photosensitive composition contains: as component A, a polymerizable monomer having three or more (meth)acryloyl groups and one or more carboxy groups in each molecule thereof; as component B, a polymerizable monomer having three or more (meth)acryloyl groups and not having a carboxy group in each molecule thereof; as component C, a photopolymerization initiator; as component D, a solvent; as component N, a blocked isocyanate compound; and as component K, a polymerization inhibitor. Furthermore, the photosensitive composition is characterized in that the component A content is 10-50 mass% of the total content of both component A and component B.

Description

Photosensitive composite, the manufacture method of cured film, cured film, touch screen, touch screen display Showing device, liquid crystal indicator and organic EL display
Technical field
The present invention relates to the manufacture method of a kind of photosensitive composite, cured film, cured film, touch screen, touch screen show Device, liquid crystal indicator and organic electroluminescent (Electroluminescence, EL) display device.
Background technology
The flat faced displays such as liquid crystal indicator, organic EL display (flat panel display) are extensively made With.Recently, in the manufacturing step of these display, the damage (damage) to substrate or circuit etc., energy-saving etc. are just reduced For viewpoint, it is necessary to realize the low temperature of the heating-up temperature of various cured films in manufacturing step.
Used as this kind of curable adhensive compositions, such as disclosing in patent documentation 1 has a kind of thermosetting resin composition, its It is characterised by：Which is by unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, the free-radical polymerised compound containing epoxy radicals and list The copolymer of olefin-based unsaturated compound is formed in being dissolved in organic solvent.A kind of active energy has been recorded in patent documentation 2 The coating composition of amount line atherosclerotic type.
[prior art literature]
[patent documentation]
No. 5201066 publications of [patent documentation 1] Japanese Patent No.
[patent documentation 2] Japanese Patent Laid-Open 2000-080169 publication
The content of the invention
Invent problem to be solved
However, the heating-up temperature of the curable adhensive compositions described in patent documentation 1 is necessary for more than 200 DEG C, if in low temperature Heated under (such as less than 180 DEG C, and then less than 150 DEG C), then film strength is insufficient, in artificial perspiration resistance's fluidity etc Have problems in terms of reliability qualifications.In addition, when though the curable adhensive compositions described in patent documentation 2 have carried out hardening at subcritical temerature The evaluation of film-strength, but not to being recorded using photolithographic pattern-forming.
It is an object of the invention to solve the problem, even and if its object is to provide one kind heat at low temperature and also may be used Obtain cured film excellent in reliability and the photosensitive composite of pattern-forming can be carried out using photoetching process.Further, the present invention Purpose be provide a kind of cured film using the photosensitive composite manufacture method and cured film and use it is described The various display devices such as the touch screen and organic EL display of cured film, liquid crystal indicator, touch panel display device.
The technological means of solve problem
The problem of the present invention is by following<1>、<9>、<11>, or<15>~<18>Described means and solve Certainly.Below with preferably<2>~<8>、<10>, and<12>~<14>Recorded in the lump.
<1>A kind of photosensitive composite, it is characterised in that contain：There are more than 3 in intramolecular as composition A The polymerism list amount body of the carboxyl of (methyl) acryloyl group and more than 1, there are more than 3 in intramolecular as composition B (methyl) acryloyl group and with the polymerism list amount body of carboxyl, the Photoepolymerizationinitiater initiater as composition C, as components D Solvent, as the blocked isocyanate compound and the polymerization inhibitor as composition K of composition N；And relative to composition A and into Divide the total content of B, the content of composition A is 10 mass %～50 mass %.
<2>According to<1>Described photosensitive composite, wherein relative to the total solid content of photosensitive composite, into The content for dividing N is 0.1 mass %～20 mass %.
<3>According to<1>Or<2>Described photosensitive composite, wherein relative to composition A and the total content of composition B, into The content for dividing A is 10 mass %～30 mass %.
<4>According to<1>Extremely<3>Any one of described in photosensitive composite, which is also containing the alkoxyl as composition S Silane compound.
<5>According to<1>Extremely<4>Any one of described in photosensitive composite, which is also containing the inorganic grain as composition E Son.
<6>According to<5>Described photosensitive composite, wherein relative to the total solid content of photosensitive composite, into The content for dividing E is 10 mass %～40 mass %.
<7>According to<1>Extremely<6>Any one of described in photosensitive composite, wherein relative to photosensitive composite The total content of total organic solid composition, composition A and composition B is 30 mass %～99 mass %.
<8>According to<1>Extremely<7>Any one of described in photosensitive composite, wherein relative to photosensitive composite Total solid content, the content of component of polymer is below 10 mass %.
<9>A kind of manufacture method of cured film, which at least sequentially includes step 1～step 5,
Step 1：Application step, by basis<1>Extremely<8>Any one of described in photosensitive composite coat substrate On；
Step 2：Solvent removal step, removes solvent from the photosensitive composite being coated with；
Step 3：Step of exposure, is carried out at least a portion for eliminating the photosensitive composite of solvent using actinic ray Exposure；
Step 4：Development step, is developed to exposed photosensitive composite using aqueous developer solution；And
Step 5：Heat treatment step, carries out heat treatment to developed photosensitive composite.
<10>According to<9>Heat treatment temperature in the manufacture method of described cured film, wherein step 5 be 80 DEG C～ 180℃。
<11>A kind of cured film, which is to make basis<1>Extremely<8>Any one of described in photosensitive composite hardening and Into.
<12>According to<11>Described cured film, which is interlayer dielectric or outer film.
<13>According to<11>Or<12>Described cured film, which is the outer film of touch screen.
<14>According to<11>Extremely<13>Any one of described in cured film, its be on unit (on-cell) structure touch Screen uses outer film.
<15>A kind of touch screen, which has basis<11>Extremely<14>Any one of described in cured film.
<16>A kind of touch panel display device, which has basis<11>Extremely<14>Any one of described in cured film.
<17>A kind of liquid crystal indicator, which has basis<11>Or<12>Described cured film.
<18>A kind of organic EL display, which has basis<11>Or<12>Described cured film.
The effect of invention
According to the present invention, it is possible to provide even if a kind of heating at low temperature can also obtain cured film excellent in reliability and can The photosensitive composite of pattern-forming is carried out using photoetching process.Further, the present invention can provide a kind of using the photonasty group The manufacture method and cured film of the cured film of compound and touch screen and organic EL display using the cured film, liquid The various display devices such as crystal device, touch panel display device.
Description of the drawings
Fig. 1 represents the composition concept map of of organic EL display, and represents bottom-emission (bottom Emission) the constructed profile of the substrate in the organic EL display of type, with planarization film 4.
Fig. 2 represents the composition concept map of of liquid crystal indicator, and represents the active matrix in liquid crystal indicator The constructed profile of substrate, with the cured film 17 as interlayer dielectric.
Fig. 3 represents the composition concept map of of the liquid crystal indicator with touch screen function.
Fig. 4 represents the composition concept map of another of the liquid crystal indicator with touch screen function.
Specific embodiment
Hereinafter, present disclosure is described in detail.The explanation of the constitutive requirements below recorded is sometimes according to this The representative embodiment of invention is carrying out, but the present invention is not limited to this kind of embodiment.Furthermore, illustrate in the application In book, "～" is to use as the connotation of lower limit and higher limit comprising numerical value described before and after which.In addition, of the invention In so-called organic EL element, refer to organic electroluminescent device.
In the statement of group (atomic group) in this manual, the statement for being substituted and being unsubstituted is not recorded comprising not Group with substituent group (atomic group), and also comprising the group (atomic group) with substituent group.Such as so-called " alkyl ", no Only comprising the not alkyl (alkyl being unsubstituted) with substituent group, and (it is substituted comprising the alkyl with substituent group Alkyl).
Furthermore, in this specification, " (methyl) acrylate " represents acrylate and methacrylate, " (methyl) third Olefin(e) acid " represents acrylic acid and methacrylic acid, and " (methyl) acryloyl group " represents acryloyl group and methylacryloyl.
In addition, in the present invention, " quality % " and " weight % " is synonymous, and " mass parts " are contained for identical with " weight portion " Meaning.
In addition, in the present invention, the combination of preferred configuration is more preferably.
In the present invention, with regard to component of polymer, its molecular weight is by with tetrahydrofuran (Tetrahydrofuran, THF) work For solvent when the polystyrene that determined of gel permeation chromatography (Gel Permeation Chromatography, GPC) change The weight average molecular weight of calculation.
(photosensitive composite)
The photosensitive composite (hereinafter also referred to as " photosensitive composite " or " compositionss ") of the present invention is characterised by Contain：As the polymerism list with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular of composition A Body is measured, be there is (methyl) acryloyl group of more than 3 in intramolecular as composition B and be there is no the polymerism list amount of carboxyl Body, the Photoepolymerizationinitiater initiater as composition C, the solvent as components D, the blocked isocyanate compound as composition N and work For the polymerization inhibitor of composition K；And relative to composition A and the total content of composition B, the content of composition A is 10 mass %～50 matter Amount %.
The photosensitive composite of the present invention also can also containing the alkoxysilane compound containing trialkylsilyl group in molecular structure as composition S and as composition E The other compositions such as inorganic particulate.
The photosensitive composite of the present invention preferably can carry out pattern-forming by using the photoetching process of alkaline-based developer.Again Person, when by using the photoetching process of alkaline-based developer to carry out the situation of pattern-forming to the photosensitive composite of the present invention, institute The pattern of formation is the pattern of the minus that photographic department is remained in a pattern.
Specifically, the compositionss containing following component are illustrated as specific embodiment.
<1st embodiment>
Composition A：The polymerism list amount with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular Body
Composition B：There is (methyl) acryloyl group of more than 3 in intramolecular and there is no the polymerism list amount body of carboxyl
Composition C：Photoepolymerizationinitiater initiater
Components D：Solvent
Composition N：Blocked isocyanate compound
Composition K：Polymerization inhibitor
<2nd embodiment>
Composition A：The polymerism list amount with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular Body
Composition B：There is (methyl) acryloyl group of more than 3 in intramolecular and there is no the polymerism list amount body of carboxyl
Composition C：Photoepolymerizationinitiater initiater
Components D：Solvent
Composition E：Inorganic particulate
Composition N：Blocked isocyanate compound
Composition K：Polymerization inhibitor
<3rd embodiment>
Composition A：The polymerism list amount with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular Body
Composition B：There is (methyl) acryloyl group of more than 3 in intramolecular and there is no the polymerism list amount body of carboxyl
Composition C：Photoepolymerizationinitiater initiater
Components D：Solvent
Composition N：Blocked isocyanate compound
Composition K：Polymerization inhibitor
Composition S：Alkoxysilane compound containing trialkylsilyl group in molecular structure
<4th embodiment>
Composition A：The polymerism list amount with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular Body
Composition B：There is (methyl) acryloyl group of more than 3 in intramolecular and there is no the polymerism list amount body of carboxyl
Composition C：Photoepolymerizationinitiater initiater
Components D：Solvent
Composition E：Inorganic particulate
Composition N：Blocked isocyanate compound
Composition K：Polymerization inhibitor
Composition S：Alkoxysilane compound containing trialkylsilyl group in molecular structure
<5th embodiment>
In any one of the 1st embodiment～the 4th embodiment, further allotment has the enforcement of surfactant Mode.
The present inventor et al. carries out the result for making great efforts research, finds containing the composition A～components D, composition N and composition K； And relative to the total content of composition A and composition B, the content of composition A in the photosensitive composite of particular range, cured film can It is excellent by property, and pattern-forming can be carried out using photoetching process, so as to complete the present invention.
Though the mechanism of action of the present invention is indefinite, speculated Ru following.Think by containing composition A, carboxyl being led Enter in compositionss, thus can carry out the development in unhardened portion.Speculate in addition, now by the amount of composition A is set as specifically Scope, can carry out pattern-forming, so as to obtain cured film excellent in reliability.Furthermore, so-called cured film excellent in reliability is Refer to that the absorption of perspiration of cured film is excellent.
Hereinafter, each composition contained by photosensitive composite of the invention is illustrated.
Composition A：The polymerism list amount with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular Body
The photosensitive composite of the present invention contains as composition A in intramolecular with more than 3 (methyl) acryloyl The polymerism list amount body of the carboxyl of base and more than 1.
Composition A is the compound with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular.
Composition A can be low molecular compound, alternatively oligomer, but and non-polymer.That is, with regard to the hardness of cured film For viewpoint, the molecular weight (in the situation with molecular weight distribution, be weight average molecular weight) of composition A be 10,000 with Under, preferably 5, less than 000, and then preferably 3, less than 000.
Composition A is in intramolecular with more than 3 (methyl) acryloyl group.(the first that intramolecular (intramolecular) has Base) number of acryloyl group is preferably 3～15, more preferably 3～10, and then preferably 3～7.
If the number of (methyl) acryloyl group is in the scope, hardness and reactivity are excellent.
As long as composition A has acryloyl (- C (=O)-CH=CH2) base and the methyl for adding up to more than 3 in an intramolecular Acryloyl group (- C (=O)-C (CH3)=CH2), it is however preferred to have add up to more than 3 acryloxy (- O-C (= O)-CH=CH2) and methacryloxy (- O-C (=O)-C (CH3)=CH2).Additionally, it is preferred that being with the third of more than 3 Enoyl-, more preferably with the acryloxy of more than 3.
Compared with methylacryloyl, acryloyl group is preferred for the excellent viewpoint of hardening (reactivity).In addition, just Reactivity is excellent and for synthesizing easy viewpoint, preferably (methyl) acryloxy.
Composition A is in intramolecular (intramolecular) with the carboxyl of more than 1.The number of one intramolecular carboxyl is preferably 1 ～6, more preferably 1～3, and then preferably 1 or 2, especially preferably 1.
If the number of the carboxyl that an intramolecular of composition A has is in the scope, developability and base material adhesion It is excellent, therefore it is preferred that.
Furthermore, the carboxyl that composition A has can forming salt.The cation of forming salt is preferably organic cation chemical combination Thing, transition metal coordination complexes cation or metal cation.Organic cation compound can be enumerated：Level Four ammonium sun from Son, level Four pyridylium, level Four quinoline cation, phosphonium cation, Iodonium cationes, sulfonium cation etc..Transition metal sun Ion can illustrate the compound described in No. 279143 publications of Japanese Patent No..Metal cation can be illustrated：Na+、K+、Li+、Ag +, Fe2+, Fe3+, Cu+, Cu2+, Zn2+, Al3+, Ca2+ etc..
Furthermore, composition A is not preferably with the acidic group in addition to the carboxyl.Acidic group in addition to carboxyl can illustrate sulfonic acid Base, phosphate etc..If with the acidic group in addition to carboxyl, there is the situation of base material adhesion reduction.
Composition A is the ester of polyol and unsaturated carboxylic acid, and preferably makes carboxylic acid anhydrides with polyol Unreacted hydroxyl reaction and there is the polymerism list amount body of acidic group (carboxyl), especially preferably polyol be Ji Wusi Alcohol and/or dipentaerythritol person.
Composition A for example can by by anhydride addition in more than 3 (methyl) acryloyl group and hydroxyl compound Obtain on (hereinafter also referred to " multifunctional (methyl) acrylate of hydroxyl ").
Multifunctional (methyl) acrylate of hydroxyl can illustrate the polyol with the hydroxyl of more than 4 and (methyl) Acrylic acid ester.
Polyol with the hydroxyl of more than 4 is preferably aliphatic polyhydroxy compound, specifically, can example Show：Two glycerol, two-trimethylolethane, two-trimethylolpropane, two-tri hydroxy methyl butane, two-Trimethylolhexane, season Penta tetrol, dipentaerythritol, tripentaerythritol etc..In these, preferably tetramethylolmethane, dipentaerythritol.
In addition, polyol can use the alkylene oxide addition product of the polyol of the illustration, alkylene oxide can Illustrate：Oxirane, expoxy propane etc..
As long as the manufacture method of hydroxyl polyfunctional acrylic ester suitably adopts known method, it is not particularly limited. Specifically, the method by polyol and (methyl) acrylic acid heated and stirred can be illustrated under acidic catalyst.Acid Property catalyst can be enumerated：Sulphuric acid, p-methyl benzenesulfonic acid and methanesulfonic acid etc..As long as in addition, reaction temperature is according to the compound for being used And purpose suitably sets, preferably 70 DEG C～140 DEG C.If in the temperature range, being then swift in response, and stably enter Row reaction, so as to the generation or gelation of impurity are suppressed.
Preferably in reaction, the organic solvent low with the dissolubility of the water generated in esterification is used, is simultaneously made Water azeotropic one side promotes dehydration.Preferred organic solvent can for example be enumerated：The aromatic hydrocarbons such as toluene, benzene and dimethylbenzene, hexane and The aliphatic hydrocarbons such as heptane, and the ketone such as methyl ethyl ketone and Ketohexamethylene etc..In addition, organic solvent also can after the reaction by decompression And distill and remove.
In addition, (methyl) acrylic ester polymerization in order to prevent gained, can add polymerization inhibitor in reactant liquor.It is this kind of Polymerization inhibitor can for example be enumerated：Hydroquinone, hydroquinone monomethyl ether, 2,6- di-t-butyls paracresol and phenothiazine etc..
Composition A is obtained with the reaction of anhydride by multifunctional (methyl) acrylate of the hydroxyl.
Anhydride can be enumerated：Succinic anhydride, 1- dodecenylsuccinic acid acid anhydrides, maleic anhydride, glutaric anhydride, itaconic anhydride, neighbour Phthalate anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrochysene neighbour's benzene two Formic anhydride, methyl tetrahydrophthalic anhydride, Nadic anhydride, methylendomethylenetetrahydrophthalic tetrahydrochysene O-phthalic Anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabromophthalic anhydride and trimellitic anhydride etc. have 1 anhydride in same intramolecular The compound of base, and pyromellitic dianhydride, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, sulfobenzide. four Carboxylic acid dianhydride, benzophenone tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides, diphenyl ether tetracarboxylic anhydride and inclined benzene three (commercially available product for example has the trade name that new Japan Chemical (stock) is manufactured to keep house moral (Rikacid) TMEG- to formic anhydride glycol ester Etc. 100) there is the compound of 2 anhydride groups in same intramolecular.
In these, preferably there is in same intramolecular the compound of 1 anhydride group.
As long as the manufacture method of composition A is according to well-established law.
For example, can enumerate in the presence of a catalyst, make multifunctional (methyl) acrylate of hydroxyl with carboxylic acid anhydrides at 60 DEG C 1 hour～20 hours method etc. is reacted at～110 DEG C.The catalyst during situation, can enumerate：N, N- dimethyl benzyl amine, Triethylamine, tri-n-butylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyl triethyl ammonium bromide, 4 bromide, acetyl group Trimethylammonium bromide and Zinc Oxide etc..
Composition A is preferably the compound represented by formula A-1 or the compound represented by formula A-2.
[changing 1]
In formula A-1, X1 separately represents acryloxy or methacryloxy, and Wl represents the Asia of carbon number 1～6 Alkyl, the alkenylene of carbon number 2～6 or phenylene.
In formula A-2, X2 separately represents hydrogen atom, the alkyl of carbon number 1～6, acryloxy or methacryl Epoxide, is present in the X2 of 5, and at least three are acryloxy or methacryloxy, and W2 represents the alkylene of carbon number 1～6 Base, the alkenylene of carbon number 2～6 or phenylene.
In formula A-1, X1 is preferably acryloxy.
In formula A-1, W1 represents the alkylidene of carbon number 1～6, the alkenylene of carbon number 2～6 or phenylene, the Asia of carbon number 1～6 Alkyl can be any one of straight-chain, branch-like, ring-type.The alkylidene is preferably carbon number 2～6, can illustrate：Ethylidene, Asia Propyl group, butylidene, amyl group, hexylidene, cyclohexylidene.
In formula A-1, W1 is preferably the alkylidene of carbon number 1～6, the more preferably alkylidene of carbon number 2～6, and then is preferably The alkylidene of carbon number 2 or 3, especially preferably ethylidene.
In formula A-2, exist in the X2 of 5, at least three represent acryloxy or methylacryloyl, preferably propylene Acyloxy.Furthermore, exist in the X2 of 5,3～5 is acryloxy or methacryloxy, preferably 4～5 For acryloxy or methacryloxy, preferably 5 is acryloxy or methacryloxy.
In addition, the X2 in addition to acryloxy or methacryloxy represents the alkyl of hydrogen atom or carbon number 1～6. The alkyl of carbon number 1～6 can be the alkyl of any one of straight-chain, branch-like, ring-type.In these, except (methyl) acryloxy X2 in addition is preferably the alkyl of hydrogen atom or carbon number 1～4, more preferably hydrogen atom, methyl or ethyl, and then preferably hydrogen is former Son.
In formula A-2, the W1 in W2 and formula 1 is synonymous, and preferred scope is also identical.
Composition A can also use the product for having listed, for example, synthesize the modified by polyacid acrylic acid that (stock) is manufactured as East Asia Oligomer, can enumerate：M-510, M-520, TO-2349, TO-2359 of sieve Ah Nice (Aronix) (registered trade mark) series etc..
Composition A can be used alone one kind, also can simultaneously with two or more.
Relative to the total organic solid composition of photosensitive composite, the content of composition A is preferably 3 mass %～49.5 matter Amount %, more preferably 3 mass %～45 mass %, and then preferably 5 mass %～40 mass %, most preferably 10 mass %～ 35 mass %.
Furthermore, " solid constituent " in the present invention in so-called photosensitive composite, refer to except the volatility such as organic solvent into Composition beyond point.In addition, so-called " organic solid composition ", refers to and the volatility such as organic solvent is removed from photosensitive composite The composition of the inorganic constituentss such as composition, inorganic particulate.
Composition B：There is (methyl) acryloyl group of more than 3 in intramolecular and there is no the polymerism list amount body of carboxyl
The photosensitive composite of the present invention contains as composition B in intramolecular with more than 3 (methyl) acryloyl Base and not the polymerism list amount body with carboxyl.Composition B is with more than 3 (methyl) propylene in intramolecular (intramolecular) Acyl group and the polymerism list amount body different from composition A.Composition B does not have carboxyl in intramolecular, does not preferably have other acid yet Base, other acidic groups can illustrate sulfonic group, phosphate etc..
Composition B can be low molecular compound, alternatively oligomer, and non-polymer.That is, with regard to cured film hardness sight For point, the molecular weight (in the situation with molecular weight distribution, be weight average molecular weight) of composition B is 10, less than 000, Preferably 5, less than 000, and then preferably 3, less than 000.
Composition B is in intramolecular with more than 3 (methyl) acryloyl group.Preferably there is 3～15 (methyl) acryloyl Base, more preferably with 3～10, and then preferably with 3～6.By being set as the composition, the present invention can be further played Effect.
Composition B can suitably select the compound being applied in this kind of compositionss and use, for example, can enumerate Japan Patent special Open the paragraph of the composition or Japanese Patent Laid-Open 2006-64921 publication described in the paragraph 0011 of 2006-23696 publications These are recorded with more than 3 (methyl) acryloyl group person in intramolecular in composition described in 0031～paragraph 0047 It is incorporated to into present specification.
Composition B preferably illustrates (methyl) acrylate of polyol, specifically, can enumerate：Ji Wusi Alcohol three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta Tetrol six (methyl) acrylate, three ((methyl) acryloyl-oxyethyl) isocyanuric acid ester, trimethylolpropane tris (methyl) Acrylate, tetramethylolmethane four (methyl) acrylated epoxy ethane (Ethylene Oxide, EO) modified body, dipentaerythritol Six (methyl) acrylate EO modified bodies etc..
Composition B can use the product for having listed, for example, can enumerate：Sieve Ah Nice (Aronix) (registered trade mark) M-309, Ah Luo Nisi (Aronix) (registered trade mark) M-400, sieve Ah Nice (Aronix) (registered trade mark) M-405, sieve Ah Nice (Aronix) (registered trade mark) M-450, sieve Ah Nice (Aronix) (registered trade mark) M-7100, sieve Ah Nice (Aronix) (note Volume trade mark) M-8030, sieve Ah Nice (Aronix) (registered trade mark) M-8060, sieve Ah Nice (Aronix) (registered trade mark) TO- 1382nd, sieve Ah Nice (Aronix) (registered trade mark) TO-1450 (East Asia synthesis (stock) manufacture), Ka Yala get (KAYARAD) TMPTA, Ka Yala get (KAYARAD) DPHA, Ka Yala get (KAYARAD) DPCA-20, Ka Yala get (KAYARAD) DPCA- 30th, Ka Yala get (KAYARAD) DPCA-60, Ka Yala get (KAYARAD) DPCA-120 (Japanese chemical medicine (stock) manufacture), than this Gram (Biscoat) 295, than this gram (Biscoat) 300, than this gram (Biscoat) 360, than this gram (Biscoat) GPT, than this Gram (Biscoat) 3PA, than this gram (Biscoat) 400 (Osaka Organic Chemical Industry (stock) manufacture) etc..
Furthermore, even if being the compound equivalent to composition B, also will be equivalent to aftermentioned alkoxysilane compound containing trialkylsilyl group in molecular structure person and be considered as alkane TMOS compound.
<(methyl) propenoic methyl carbamate>
(methyl) propenoic methyl carbamate can be used in the present invention as composition B.
(methyl) propenoic methyl carbamate that can be used in the present invention can illustrate the addition for using isocyanates and hydroxyl Reaction and manufacture carbamate addition polymerization compound, and can illustrate Japanese Patent Laid-Open No. Sho 51-37193 publication, Acrylic described in Japanese Patent Laid-fair 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication Esters, these records are incorporated to into present specification.
For hardening the viewpoint of film hardness, the molecular weight of (methyl) propenoic methyl carbamate is preferably 500～10, 000, more preferably 650～6,000, and then preferably 800～3,000.
By being set as this kind of composition, and more effectively play the effect of the present invention.
(methyl) acryloxy base in (methyl) propenoic methyl carbamate can be acryloxy, methacryl Any one of epoxide, alternatively both, preferably acryloxy.
The number of (methyl) acryloxy in (methyl) propenoic methyl carbamate is preferably more than 3, more preferably 6 More than, and then preferably more than 10.If the form, then more effectively play the effect of the present invention.
In addition, the upper limit of the number of (methyl) acryloxy there is no particular restriction, preferably less than 50, more preferably For less than 30, and then preferably less than 20.
The curable adhensive compositions of the present invention can only containing a kind of (methyl) propenoic methyl carbamate, also can containing two kinds with On.
(methyl) acryloxy in (methyl) propenoic methyl carbamate can be acryloxy, methacryloxypropyl Any one of base, alternatively both, preferably acryloxy.
There is no particular restriction for the number of the amino-formate bond in (methyl) propenoic methyl carbamate, and preferably 1～30, More preferably 1～20, and then preferably 2～10, especially preferably 2～5, most preferably 2 or 3.
(methyl) propenoic methyl carbamate is preferably aliphatic (methyl) propenoic methyl carbamate.
In addition, (methyl) propenoic methyl carbamate is preferably with isocyanuric acid ring structure.
In addition, core part of (methyl) propenoic methyl carbamate preferably comprising the amino-formate bond with more than 1, And the compound of core part and the end section with more than 1 (methyl) acryloxy is bonded to, more preferably described On core part, bond has the compound of the end section of more than 2, and then preferably on the core part, bond has 2 The compound of～5 end sections, especially preferably on the core part, bond has 2 or 3 end sections Compound.
(methyl) propenoic methyl carbamate is preferably at least with the group represented by following formula Ae-1 or formula Ae-2 Compound, the compound more preferably at least with the group represented by following formula Ae-1.In addition, (methyl) acrylic-amino first Acid esters is more preferably with more than 2 selected from the group institute group represented by the group and formula Ae-2 represented by following formula Ae-1 Into group in group compound.
In addition, the end section in (methyl) propenoic methyl carbamate is preferably following formula Ae-1 or formula Ae-2 institute The group of expression.
[changing 2]
In formula Ae-1 and formula Ae-2, R separately represents acrylic or methacrylic acid group, swash part represent with The binding site of other structures.
In addition, (methyl) propenoic methyl carbamate is preferably at least with the base represented by following formula Ac-1 or formula Ac-2 The compound of group, the compound more preferably at least with the group represented by following formula Ac-1.
In addition, the core part in (methyl) propenoic methyl carbamate is preferably following formula Ac-1 or formula Ac-2 institute table The group for showing.
[changing 3]
In formula Ac-1 and formula Ac-2, L1～L4 separately represents the bivalent hydrocarbon radical of carbon number 2～20, and swash part represents With the binding site of other structures.
L1～L4 is separately preferably the alkylidene of carbon number 2～20, and the more preferably alkylidene of carbon number 2～10 enters And the preferably alkylidene of carbon number 4～8.In addition, the alkylidene can also have branch or ring structure, preferably straight chain alkylene Base.
In addition, (methyl) propenoic methyl carbamate is especially preferably formula Ac-1 or the group represented by formula Ac-2 and choosing The compound of 2 or 3 group bonds in the group constituted by the group represented by free style Ae-1 and formula Ae-2.
(methyl) propenoic methyl carbamate for preferably using in the present invention illustrated below, but the present invention do not limited certainly Due to these compounds.
[changing 4]
[changing 5]
[changing 6]
In addition, (methyl) propenoic methyl carbamate that can be used in the present invention can be illustrated uses isocyanates with hydroxyl Additive reaction and the carbamate addition polymerization compound that manufactures, and it is public to illustrate Japanese Patent Laid-Open No. Sho 51-37193 Acrylic-amino described in report, Japanese Patent Laid-fair 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication Formate ester, these records are incorporated to into present specification.
The commercially available product of (methyl) propenoic methyl carbamate can be illustrated：Can the U- that obtains of Zi Xinzhong villages chemical industry (stock) 6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, U-10PA, UA-53H, UA-33H (are registered trade mark), or UA-306H, UA-306T, UA-306I, the UA-510H that can be obtained from common prosperity society chemistry (stock), can be from BASF (BASF) company La Luomo (Laromer) UA-9048, La Luomo (Laromer) UA-9050, La Luomo (Laromer) PR9052 of acquisition, can From Daicel-Zhan Ai Bai gram forces (EBECRYL) 220 that newly (Daicel-Allnex) (stock) is obtained, Ai Bai gram forces (EBECRYL) 5129th, Ai Bai gram forces (EBECRYL) 8301, KRM8200, KRM8200AE, KRM8452 etc..
Composition B can be used alone one kind, also can simultaneously with two or more.
Relative to the total organic solid composition of photosensitive composite, the content of composition B is preferably 20 mass %～85 matter Amount %, more preferably 30 mass %～80 mass %, and then preferably 45 mass %～75 mass %.
In the present invention, relative to composition A and the total content of composition B, the content of composition A is 10 mass %～50 mass %. If relative to composition A and the total content of composition B, the content of composition A is less than 10 mass, then the amount of the carboxyl in compositionss is reduced, Developability (pattern-forming) is poor.If in addition, more than poor reliability such as 50 mass %, absorptions of perspiration.
The content of composition A is preferably 12 mass %～40 mass % relative to the total content of composition A and composition B, more preferably For 15 mass %～35 mass %, and then preferably 18 mass %～30 mass %.
In addition, in the present invention, relative to the total content of the total organic solid composition of photosensitive composite, composition A and composition B It is more than preferably 40 mass %.If the total content of composition A and composition B is in the scope, the reliability of developability and cured film Property is excellent.
30 mass % are preferably relative to the total content of the total organic solid composition of photosensitive composite, composition A and composition B ～99 mass %, more preferably 40 mass %～99 mass %, and then preferably 50 mass %～98 mass %, most preferably 60 Quality %～95 mass %.
Composition C：Photoepolymerizationinitiater initiater
The photosensitive composite of the present invention contains the Photoepolymerizationinitiater initiater as composition C.
Photoepolymerizationinitiater initiater is preferably and contains radical polymerization initiator.
In the present invention can using Photoepolymerizationinitiater initiater be can be caused by light, promote be polymerized compound.Wherein, more Preferably optical free radical polymerization initiator.
So-called " light ", as long as to give and can produce the active-energy for causing the energy planted by composition C by its irradiation Line, then there is no particular restriction, widely comprising alpha ray, gamma-rays, X-ray, ultraviolet (Ultraviolet, UV), visible ray Line, electron beam etc..In these active energy rays, preferably at least bag light with violet rays.
Photoepolymerizationinitiater initiater can for example be enumerated：Oxime ester compound, organic halogenation compound, epoxide diazole compounds, carbonyl Compound, ketal compound, aroma compounds of resting in peace, acridine compounds, organic peroxy compound, azo-compound, coumarin Compound, azido compound, metallocene compound, six aryl united imidazoles, organic boric acid compounds, disulfonic acid chemical combination Thing, salt compound, acylphosphanes (oxide) compound.In these compounds, for the aspect of sensitivity, preferably oxime ester Compound, more preferably six aryl united imidazoles, oxime ester compound.
Oxime ester compound can be used：Japanese Patent Laid-Open 2000-80068 publication, Japanese Patent Laid-Open 2001-233842 Number publication, Japanese Patent Laid 2004-534797 publication, Japanese Patent Laid-Open 2007-231000 publication, Japan Patent are special Open the compound described in 2009-134289 publications.
Compound represented by oxime ester compound preferably following formula 1 or formula 2.
[changing 7]
In formula 1 or formula 2, Ar represents aromatic series base or heteroaromatic base, and R1 represents alkyl, aromatic series base or alkoxyl, R2 Hydrogen atom or alkyl are represented, and then R2 also can be bonded with Ar bases and form ring.
Ar represents aromatic series base or heteroaromatic base, preferably closes from the cyclisation of benzene ring compound, naphthalene cycle compound or carbazole Remove the group obtained by the hydrogen atom on 1 aromatic rings in thing, naphthyl, the carbazyl of ring are more preferably formed together with R2.It is miscellaneous Hetero atom in aromatic series base is preferably enumerated：Nitrogen-atoms, oxygen atom and sulphur atom.
R1 represents alkyl, aromatic series base or alkoxyl, preferably methyl, ethyl, benzyl, phenyl, naphthyl, methoxyl group or second Epoxide, more preferably methyl, ethyl, phenyl or methoxyl group.
R2 represents hydrogen atom or alkyl, preferably hydrogen atom or the alkyl being substituted, more preferably hydrogen atom, together with Ar Form the alkyl being substituted or toluene alkylthio of ring.
In addition, Ar is preferably the group of carbon number 4～20, R1 is preferably the group of carbon number 1～30, and R2 is preferably carbon number 1 ～50 group.
Oxime ester compound and then the compound preferably represented by following formula 3, formula 4 or formula 5.
[changing 8]
In 3～formula of formula 5, R1 represents alkyl, aromatic series base or alkoxyl, and X represents-CH2- ,-C2H4- ,-O- or S-, R3 point Halogen atom is not independently represented, R4 separately represents the alkyl-substituted amino of alkyl, phenyl, Jing, arylthio, alkane sulfur Base, alkoxyl, aryloxy group or halogen atom, R5 represent hydrogen atom, alkyl or aryl, and R6 represents alkyl, n1 and n2 independently Ground represents 0～6 integer, and n3 represents 0～5 integer.
R1 represents alkyl, aromatic series base or alkoxyl, and preferably R11-X '-alkylidene-(R11 is represented represented group Alkyl or aryl, X ' represent sulphur atom or oxygen atom).R11 is preferably aryl, more preferably phenyl.As the alkyl and virtue of R11 Base also can Jing halogen atoms (preferably fluorine atom, chlorine atom or bromine atoms) or alkyl replacement.
X is preferably sulphur atom.
R3 and R4 can be on aromatic rings optional position enterprising line unit knot.
R4 represents that the alkyl-substituted amino of alkyl, phenyl, Jing, arylthio, alkylthio group, alkoxyl, aryloxy group or halogen are former Son, preferably alkyl, phenyl, arylthio or halogen atom, more preferably alkyl, arylthio or halogen atom, and then be preferably Alkyl or halogen atom.Alkyl is preferably the alkyl of carbon number 1～5, more preferably methyl or ethyl.It is former that halogen atom is preferably chlorine Son, bromine atoms or fluorine atom.
In addition, the carbon number of R4 is preferably 0～50, more preferably 0～20.
R5 represents hydrogen atom, alkyl or aryl, preferably alkyl.Alkyl is preferably the alkyl of carbon number 1～5, more preferably Methyl or ethyl.Aryl is preferably the aryl of carbon number 6～10.
R6 represents alkyl, the preferably alkyl of carbon number 1～5, more preferably methyl or ethyl.
The replacement number of the R3 on aromatic rings in n1 and n2 difference expressions 3 or formula 4, on the aromatic rings in n3 expressions 5 R4 replacement number.
N1～n3 separately be preferably 0～2 integer, more preferably 0 or 1.
The example of the oxime ester compound preferably used in the present invention described below.However, oxime used in the present invention Ester compounds are not limited to these compounds certainly.Furthermore, Me represents methyl, and Ph represents phenyl.In addition, in these compounds The cis-trans isomerism of the double bond of oxime can be any one of EZ, the alternatively mixture of EZ.
[changing 9]
[changing 10]
The example of organic halogenation compound can specifically be enumerated：If woods et al.《Japanization association publication (Bull Chem.Soc.Japan)》(42,2924 (1969)), U.S. Patent No. 3,905, No. 815 description, Japan Patent examined patent publications 46- No. 4605 publications, Japanese Patent Laid-Open No. Sho 48-36281 publication, Japanese Patent Laid-Open No. Sho 55-32070 publication, Japan Patents JP 60-239736 publication, Japanese Patent Laid-Open No. Sho 61-169835 publication, Japanese Patent Laid-Open No. Sho 61-169837 Publication, Japanese Patent Laid-Open No. Sho 62-58241 publication, Japanese Patent Laid-Open No. Sho 62-212401 publication, Japanese Patent Laid-Open Clear 63-70243 publications, Japanese Patent Laid-Open No. Sho 63-298339 publication, M.P. Hattons (M.P.Hutt)《Heterocyclic chemistry Periodical (Journal of Heterocyclic Chemistry)》Compound described in (1 (No3), (1970)) etc., especially Trihalomethyl group can be enumerated to carry out replacing oxazole compounds, s-triazine.
The example of six aryl united imidazoles can for example be enumerated：Japanese Patent Laid-fair 6-29285 publication, the U.S. are special Described in each description of profit the 3,479,185th, U.S. Patent No. 4,311,783, U.S. Patent No. 4,622,286 etc. Various compounds.
Acylphosphanes (oxide) compound can illustrate monoacylphosphine oxides compound and bisacylphosphine oxides compound, Specifically, can for example enumerate：Gorgeous good solid (Irgacure) 819 of BASF (BASF) company manufacture, up to Luo Gu (Darocure) 4265, up to Luo Gu (Darocure) TPO etc..
Photoepolymerizationinitiater initiater can be used a kind of or is applied in combination two or more.
Relative to 100 mass parts of total solid content in compositionss, the photopolymerization in the photosensitive composite of the present invention is drawn The total amount for sending out agent is preferably 0.5 mass parts～30 mass parts, more preferably 1 mass parts～20 mass parts, and then preferably 1 mass Part～10 mass parts, especially preferably 2 mass parts～5 mass parts.
Relative to the total organic solid composition of compositionss, the content of Photoepolymerizationinitiater initiater is preferably 0.5 mass %～30 matter Amount %, more preferably 1 mass %～20 mass %, and then preferably 1 mass %～10 mass %, especially preferably 1 mass % ～5 mass %.
<Sensitizer>
In the photosensitive composite of the present invention, in addition to Photoepolymerizationinitiater initiater, can also add sensitizer.
Sensitizer absorbs actinic ray or lonizing radiation and becomes excited state.Become excited state sensitizer can by with The interaction of composition C, and the effect such as electron transfer, energy transfer, heating is produced, promote polymerization so as to cause.
The typical sensitizer that can be used in the present invention can enumerate J.V. gram of Fernanda Ribeiro (J.V.Crivello) (《Polymerization Thing scientific development (Adv.in Polymer Sci.)》(62,1, (1984))) the middle sensitizer for disclosing, can specifically enumerate：Pyrene, Perylene, acridine orange, thioxanthone, 2- chlorothiaxanthenones, benzoflavine, N- VCzs, 9,10- dibutoxy anthracenes, anthraquinone, perfume (or spice) Legumin, coumarin ketone (ketocoumarin), phenanthrene, camphorquinone, phenothiazine derivative etc..Sensitizer is preferably relative to photopolymerization Initiator and added with the ratio of 50 mass %～200 mass %.
Components D：Solvent
The photosensitive composite of the present invention contains the solvent as components D.The present invention photosensitive composite be preferably with Using the composition A as required composition, composition B, composition C and composition N described later and composition K and any condition described later dissolving It is prepared by the form of the solution in solvent.
Components D is preferably organic solvent, and the organic solvent used in the photosensitive composite of the present invention can use known Solvent, can illustrate：Ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, Propylene Glycol list Alkyl ether, Propylene Glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol Monoalkyl ether acetate class, dipropylene glycol monoalkylether class, butanediol oxalic acid esters, dipropylene glycol dialkyl ether, dipropyl Glycol monoalkyl ether acetate esters, alcohols, esters, ketone, amide-type, lactone etc..The concrete example of these organic solvents can be joined According to the paragraph 0062 of Japanese Patent Laid-Open 2009-098616 publication.
Specifically, preferably propylene glycol methyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, third Glycol monomethyl ether, 1,3 butylene glycol diacetate esters, adnoral acetate, propylene-glycol diacetate, tetrahydrofurfuryl alcohol.
For the viewpoint of coating, the boiling point of organic solvent is preferably 100 DEG C～300 DEG C, more preferably 120 DEG C～ 250℃。
The solvent that can be used in the present invention can be used alone one kind or and with two or more.It is preferably also and different with boiling point Solvent.
For being adjusted to and being suitable to the viewpoint of the viscosity being coated with, relative to 100 mass parts of total solid content of compositionss, this The content of the solvent in the photosensitive composite of invention is preferably 100 mass parts～3, more preferably 000 mass parts, 200 mass Part～2,000 mass parts, and then preferably 250 mass parts～1,000 mass parts.
The solid component concentration of photosensitive composite preferably 3 mass %～50 mass %, more preferably 20 mass %～ 40 mass %.
The viscosity of photosensitive composite is preferably 1mPas～200mPas, more preferably 2mPas～100mPa S, most preferably 3mPas～80mPas.Viscosity is for example rotated preferably with the RE-80L types that eastern machine industry (stock) manufactures Viscometer is determined at 25 DEG C ± 0.2 DEG C.Rotating speed during with regard to determining, viscosity less than be preferably in the case of 5mPas with The rotating speed of 100rpm is measured, viscosity be 5mPas less than 10mPas in the case of be preferably with 50rpm's Rotating speed is measured, viscosity be 10mPas less than 30mPas in the case of be preferably entered with the rotating speed of 20rpm Row is determined, and is preferably in the case where viscosity is more than 30mPas and is measured with the rotating speed of 10rpm.
Composition N：Blocked isocyanate compound
The photosensitive composite of the present invention contains the blocked isocyanate compound as composition N.By containing composition N, The high cured film of reliability can be obtained.Though its mechanism of action is indefinite, the heat treated after photo-hardening is thought and composition N Blocked isocyanate base by deprotection.Think, in cured film, to play a role by the NCO from composition N, with The adhesion of substrate is improved, or is interacted with moisture, salt by NCO, obtains the high cured film of reliability.
As long as blocked isocyanate compound is the compound with blocked isocyanate base, then there is no particular restriction, just For indurative viewpoint, preferably in compound of the intramolecular with more than 2 blocked isocyanate base.Closing Carbimide. The upper limit of the number of ester group is not particularly limited, and preferably less than 6.
In addition, the skeleton of blocked isocyanate compound is not particularly limited, as long as having 2 Carbimide .s in a molecule Ester group can be then any skeleton, can be aliphatic, alicyclic or aromatic polyisocyanate, for example, preferably use：2, 4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, isophorone diisocyanate, 1,6- hexa-methylenes, two Carbimide. Ester, 1,3- trimethylene diisocyanates, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4- tri-methyl hexamethylene, two Carbimide. Ester, 2,4,4- trimethyl hexamethylene diisocyanates, 1,9-, nine methylene diisocyanates, 1,10- decamethylenes, two isocyanide Acid esters, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-diethyl ether diisocyanate, diphenyl methane -4,4 '-diisocyanate, neighbour XDI, m xylene diisocyanate, xylol diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl Carbimide. Ester), hexamethylene -1,3- dimethylene diisocyanates, hexamethylene-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5- naphthalenes, two isocyanide Acid esters, PPDI, 3,3 '-xylene -4,4 '-diisocyanate, 4,4 '-diphenyl ether, two Carbimide. Ester, tetrachloro phenylene diisocyanate, norbornene alkyl diisocyanate, hydrogenation 1,3- XDIs, hydrogenation Isosorbide-5-Nitrae-diformazan The isocyanate compounds such as phenylene diisocyanate, and these compounds polymer and by derived from these compounds it is pre- The compound of the skeleton of polymers type.In these compounds, preferably to selected from toluene di-isocyanate(TDI) (Tolylene Diisocyanate, TDI) or methyl diphenylene diisocyanate (Diphenyl methane diisocyanate, MDI), six Methylene diisocyanate (Hexamethylene diisocyanate, HDI), isophorone diisocyanate (Isophorone diisocyanate, IPDI), and the group that constituted of polymer of these compounds in compound carry out The blocked isocyanate compound of protection, more preferably to selected from hexamethylene diisocyanate, isophorone diisocyanate The blocked isocyanate compound protected by compound in the group constituted by the polymer of ester and these compounds.
As long as the polymer of isocyanate compound is polymer more than dimer, then there is no particular restriction, can illustrate： Biuret body, isocyanuric acid ester body, adduction object etc., preferably biuret body.
The parent structure of the blocked isocyanate compound in the photosensitive composite of the present invention can be enumerated：It is biuret form, different Cyanurate ester type, adduct type, two functional prepolymer types etc..
The sealer for forming the enclosed construction of the blocked isocyanate compound can be enumerated：Oxime compound, lactamize Compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazoles system Compound, imide series compound etc..In these compounds, preferably oxime compound, lactam compound, phenolic compounds, alcohol Compound, amines, activity methene compound or pyrazole compound, more preferably oxime compound and lactam compound, And then preferably oxime compound, especially preferably methyl ethyl ketone oxime.
The oxime compound can enumerate oxime and ketoxime, specifically, can illustrate：Acetone oxime, formaldoxime, hexamethylene oxime, first Base ethyl ketoxime, cyclohexanone-oxime, diphenyl-ketoxime etc..
The lactam compound can illustrate epsilon-caprolactams, butyrolactam etc..
The phenolic compounds can be illustrated：Phenol, naphthols, cresol, xylenol, halogen substiuted phenol etc..
The alcoholic compound can be illustrated：Methanol, ethanol, propanol, butanol, Hexalin, ethylene glycol monoalkyl ether, Propylene Glycol list Alkyl ether, lactic acid alkyl ester etc..
The amines can enumerate primary amine and secondary amine, can be aromatic amine, aliphatic amine, cycloaliphatic amines it is arbitrary Kind, can illustrate：Aniline, diphenylamine, aziridine, polyethyleneimine etc..
The activity methene compound can be illustrated：Diethyl malonate, dimethyl malenate, ethyl acetoacetate, second Methyl acetoacetate etc..
The pyrazole compound can be illustrated：Pyrazoles, methylpyrazole, dimethyl pyrazole etc..
The mercaptan compound can be illustrated：Alkyl hydrosulfide, aryl mercaptan etc..
The blocked isocyanate compound that can be used in the photosensitive composite of the present invention can be obtained as commercially available product, example As preferably used：Crow Nat (Coronate) AP stable M, Crow Nat (Coronate) 2503, Crow Nat (Coronate) 2515, Crow Nat (Coronate) 2507, Crow Nat (Coronate) 2513, Crow Nat (Coronate) 2555, rice Leo Nat (Millionate) MS-50 (being Japanese polyurethane industry (stock) manufacture above), Plutarch Nat (Takenate) B-830, Plutarch Nat (Takenate) B-815N, Plutarch Nat (Takenate) B-820NSU, Plutarch How are Nat (Takenate) B-842N, Plutarch Nat (Takenate) B-846N, Plutarch Nat (Takenate) B-870N, Plutarch Spy (Takenate) B-874N, Plutarch Nat (Takenate) B-882N (manufacturing for Mitsui Chemicals (stock) above), Du draws Nat (Duranate) 17B-60P, Du draw Nat (Duranate) 17B-60PX, Du to draw Nat (Duranate) 17B-60P, Du Lanai Spy (Duranate) TPA-B80X, Du draw Nat (Duranate) TPA-B80E, Du to draw Nat (Duranate) MF-B60X, Du Draw Nat (Duranate) MF-B60B, Du draw Nat (Duranate) MF-K60X, Du draw Nat (Duranate) MF-K60B, Du draws Nat (Duranate) E402-B80B, Du to draw Nat (Duranate) SBN-70D, Du to draw Nat (Duranate) SBB- 70P, Du draw Nat (Duranate) K6000 (being Asahi Chemical Industry's chemistry (Asahi Kasei Chemicals) (stock) manufacture above), De Simo (Desmodule) BL1100, De Simo (Desmodule) BL1265MPA/X, De Simo (Desmodule) BL3575/ 1st, De Simo (Desmodule) BL3272MPA, De Simo (Desmodule) BL3370MPA, De Simo (Desmodule) BL3475BA/SN, De Simo (Desmodule) BL5375MPA, De Simo (Desmodule) VPLS2078/2, De Simo (Desmodule) BL4265SN, De Simo (Desmodule) PL340, De Simo (Desmodule) PL350, Su meter Du (Sumidule) BL3175 (manufacturing firmly to change bayer urethane (Sumitomo-Bayer Urethane) (stock) above) etc..
Relative to the total solid content of photosensitive composite, the blocked isocyanate in the photosensitive composite of the present invention The content of compound is preferably 0.1 mass %～20 mass %, more preferably 0.5 mass %～10 mass %, and then preferably 1 matter Amount %～5 mass %.
In addition, relative to the total organic solid composition of photosensitive composite, the closing in the photosensitive composite of the present invention The content of isocyanate compound is preferably 0.1 mass %～20 mass %, and more preferably 0.5 mass %～10 mass % is entered And preferably 1 mass %～5 mass %.
If the content of composition N is in the scope, cured film excellent in reliability can be obtained, therefore it is preferred that.
Composition K：Polymerization inhibitor
The photosensitive composite of the present invention contains the polymerization inhibitor as composition K.By containing composition K, by what is leaked Polyreaction caused by light is suppressed, and developability is excellent.So-called polymerization inhibitor, refers to the material for playing following effect： To by exposure or heat and by polymerization initiator produce polymerization initiation radical composition implement hydrogen supply (or awarding hydrogen), energy supply (or Award can), supplied for electronic (or awarding electronics) etc., inactivate polymerization initiation radical, suppress polymerization to cause.Japan Patent can for example be used Compound described in the 0154～paragraph of paragraph 0173 of JP 2007-334322 publication etc..
As the species of polymerization inhibitor, it is preferable to sensitivity descender is made using hard and not.It is this kind of polymerization retardation Agent can be enumerated：Phenothiazine, chlorpromazine (chlorpromazine), levomepromazine (levomepromazine), perphenazine (fluphenazine), double (diethylamino) fens of the phenothiazine derivative ， phenoxazines such as mellaril (thioridazine), 3,7- Oxazine -5- perchlorate (perchlorate), 5- amino -9- (dimethylamino) -10- methyl benzo [a] phenoxazine -7- Chloride, 7- (amoxy) -3H- phenoxazine -3- ketone, 5,9- diaminourea benzo [a] phenoxazine -7- acetates, 7- ethoxies The phenoxazine derivants such as base -3H- phenoxazine -3- ketone, three-p-nitrophenyl ylmethyl, diphenyl hardship diazanyl (picrylhydrazyl), the stabilized radical such as ten thousand epoxide free radical (Galvinoxyl) of jar (unit of capacitance), quinone, benzoquinone, chloranil, 2,5- Two-chloranil, 2,6-, bis--chloranils, 2,3-, bis--methylbenzoquinones, 2,5-, bis--methylbenzoquinones, methoxyl group benzoquinone, methylbenzoquinone, Tetrabromo-quinone, tetrachloroquinone, tetramethyl-benzoquinone, trichlorine benzoquinone, trimethylbenzoquinone, amyl group quinone, amoxy hydroquinone, 2,5- The quinones such as di-t-butyl hydroquinone, 2,5- diphenyl -1,4-benzoquinone, alpha-Naphthol, 2- nitro -1- naphthols, betanaphthol, 1- nitros - The aphthols such as beta naphthal, 4- methoxyphenols, 4- thanatols, hydroquinone, phenol, tert-butyl catechol, methyl pair Benzodiazepiness, normal-butyl phenol, hydroquinone list propyl ether, tert-butyl group cresol, paracresol, 2,6- di-t-butyl paracresol, adjacent benzene two Phenol resorcinol, o- tert-butyl phenol, 2,6-, bis--p methoxy phenols, 2,6- di-t-butyl phenol, 2,4- di-t-butyls Phenol, 3,5- di-t-butyl phenol, 3,5- di-t-butyl -4-HBAs, N, and N '-bis- -3- (3 ', 5 ',-two-tertiary fourth Base -4- hydroxy phenyls) propiono pregnancy diamidogen, 2,2 '-di-2-ethylhexylphosphine oxide (6- t-butyl-p-cresols), n-octadecane base -3- (4- Hydroxyl -3 ', 5 '-di-t-butyl phenyl) propionic ester, (the 4- hydroxy-3-methyl -5- tert-butyl groups) benzyl malonic acid distearyl ester, 2, 4,6- tri--tert-butyl phenols, 1,6- hexanediol-bis- [3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic ester], triethylene glycol - Double [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic esters], bis- [3- (3, the 5- di-t-butyl -s of 2,2- sulfur-diethylidenes - 4- hydroxy phenyls) propionic ester], double [1, the 1- dimethyl -2- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyl oxygen of 3,9- Base ethyl -2,4,8,10- tetra- oxaspiro [5,5] hendecanes, 2,2 '-ethylidene-bis--(2,4- di-t-butyl phenol), 1,1,3- Three-(2- methyl -4- hydroxyl -5- tert-butyl-phenyl butane, 1,3,5- trimethyl -2,4,6- tri- (3,5- di-t-butyl -4- hydroxyls Benzyl) benzene, three (3,5- di-t-butyl -4- hydroxybenzyl) isocyanates, three [2- (3 ', 5 '-di-t-butyl -, 4 '-hydroxyl hydrogens Change-Cortex cinnamomi japonici (Ramulus Cinnamomi) acyloxy) ethyl] it is isocyanates, three (the 4- tert-butyl group -2,6- bis--methyl -3- hydroxybenzyls) isocyanates, four [sub- Methyl -3- (3 ', 5 '-di-t-butyl -, 4 '-hydroxy phenyl) propionic ester] phenol such as-methane, 2,4-DNP, adjacent nitre The nitrophenyl phenolics such as base phenol, metanitrophenol, paranitrophenol, gallic acid, gallicin, propylgallate, The pigments such as the Galla Turcica (Galla Helepensis) acids such as isoamyl gallate, methylene blue, peacock green, betanaphthyl amine, N- nitroso-group cyclohexyl amine salt, The amines such as two-p-fluorophenyl amine, pyrogallol, single-benzyl ether, benzophenone, triphenylphosphine, Cu-lyt., phenothiazine, chloranil (chloranil), pyridine, Nitrobenzol, dinitro benzene, para-totuidine, picric acid, methyl salicylate etc..
Polymerization inhibitor can be especially preferably illustrated in phenothiazine, phenoxazines, hindered amine and these derivant It is at least one.
Phenothiazine and its derivant can be illustrated：Phenothiazine, double (α-methylbenzyl) phenothiazine, 3,7- dioctyl phenothiazine, Double (α-dimethylbenzyl) phenothiazine, preferably phenothiazine.
Phenoxazine and its derivant can be illustrated：Phenoxazine, 3,7- pair (diethylamino) phenoxazine -5- perchlorate, 5- amino -9- (dimethylamino) -10- methyl benzo [a] phenoxazine -7- chlorides, 7- (amoxy) -3H- phenoxazine -3- Ketone, 5,9- diaminourea benzo [a] phenoxazine -7- acetates, preferably 7- ethyoxyl -3H- phenoxazine -3- ketone, phenoxazine.
Hindered amine and its derivant can be illustrated：Intelligence Ma Suobu (CHIMASSORB) 2020FDL, Supreme Being slave refined (TINUVIN) 144th, refined (TINUVIN) 765, Supreme Being slave of Supreme Being slave refined (TINUVIN) 770 (manufacturing for BASF (BASF) company above), preferably Supreme Being slave refined (TINUVIN) 144.
Relative to the total solid content of photosensitive composite, the content of the composition K in the photosensitive composite of the present invention is excellent Elect the scope of 0.01 mass %～0.5 mass %, the more preferably scope of 0.1 mass %～0.5 mass % as.It is poly- by adjustment The allotment amount of inhibitor is closed, can lossless sensitivity ground raising analyticity.
Relative to the total organic solid composition of photosensitive composite, the composition K's in the photosensitive composite of the present invention contains Amount is preferably the scope of 0.01 mass %～0.5 mass %, the more preferably scope of 0.05 mass %～0.5 mass %.Pass through The allotment amount of adjustment polymerization inhibitor, can lossless sensitivity ground raising analyticity.
Composition E：Inorganic particulate
The photosensitive composite of the present invention also can be containing the inorganic particulate as composition E.By containing inorganic particulate, hardening The hardness of film becomes more excellent.
In the present invention, the mean diameter of inorganic particulate used is preferably 1nm～200nm, more preferably 5nm～100nm, Most preferably 5nm～50nm.Mean diameter is referred to using ultramicroscope to be obtained to determine the particle diameter of any 200 particles Arithmetic mean of instantaneous value.In addition, in the shape aspheric situation of particle, longest edge is set as particle diameter.
In addition, for the viewpoint of the hardness of cured film, the voidage of inorganic particulate is preferably less than 10%, more preferably Less than 3%, most preferably and tight.The voidage of particle is the profile image by obtained by ultramicroscope of 200 particles Gap and the area ratio of overall particle arithmetic mean of instantaneous value.
Inorganic particulate is preferably containing beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), gadolinium (Gd), terbium (Tb), dysprosium (Dy), ytterbium (Yb), lutecium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), molybdenum (Mo), tungsten (W), zinc (Zn), boron (B), aluminum (Al), silicon (Si), germanium (Ge), stannum (Sn), lead (Pb), antimony (Sb), bismuth (Bi), tellurium (Te) equiatomic metal oxide particle, more preferably silicon oxide, titanium oxide, titanium composite oxide, Zinc Oxide, zirconium oxide, Indium/tin-oxide, antimony/tin-oxide, and then preferably silicon oxide, titanium oxide, titanium composite oxide, zirconium oxide, with regard to particle Stability, easy availability, the hardness of cured film, the transparency, refractive index adjustment etc. be for viewpoint, especially preferably silicon oxide or Titanium oxide.
Silicon oxide preferably enumerates silicon dioxide, it may be more preferable to which silicon dioxide granule is enumerated on ground.
As long as silicon dioxide granule is the particle of the inorganic oxide containing silicon dioxide, then special problem is had no, preferably It is the particle containing silicon dioxide or its hydrate as main constituent (preferably more than 80 mass %).The particle can also contain Aluminate is used as a small amount of composition (e.g., less than 5 mass %).Sometimes the aluminate for containing as a small amount of composition can enumerate aluminic acid Sodium, potassium aluminate etc..In addition, silicon dioxide granule also can be containing nothings such as sodium hydroxide, potassium hydroxide, Lithium hydrate, ammonium hydroxide The organic salt such as machine salt or Tetramethylammonium hydroxide.The example of this kind of compound can illustrate silica sol.
There is no particular restriction for the disperse medium of silica sol, can be appointing for water, organic solvent and these mixture It is a kind of.These disperse medium can be used alone one kind, also can simultaneously with two or more.
In the present invention, particle also can be in the form of dispersion liquid for using, and the dispersion liquid is by appropriate dispersion Used in agent and solvent, the mixing arrangement such as ball mill, rod mill makes particle carry out mixing dispersion and preparing.Furthermore, it is of the invention In photosensitive composite, silica sol is not necessarily present with colloidal state.
Allocate inorganic particulate situation when, for the viewpoint of hardness, relative to photosensitive composite total solid into Point, the content of inorganic particulate is preferably more than 1 mass %, more than more preferably 5 mass %, and then preferably 10 mass % with On.Additionally, it is preferred that be below 80 mass %, it is below more preferably 50 mass %, and then below preferably 40 mass %, especially excellent Elect below 30 mass % as.
Inorganic particulate only containing one kind can also can contain two or more.When containing two or more situations, which is preferably Total amount becomes the scope.
Composition S：Alkoxysilane compound containing trialkylsilyl group in molecular structure
The photosensitive composite of the present invention is preferably containing the alkoxysilane compound containing trialkylsilyl group in molecular structure as composition S.If using alcoxyl Base silane compound, then can improve the adhesion of the film and substrate formed by the photosensitive composite of the present invention.
As long as alkoxysilane compound containing trialkylsilyl group in molecular structure is the group that alkoxyl is directly bonded to silicon atom with least one Compound, then there is no particular restriction, it is however preferred to have the compound of dialkoxy silicane base and/or trialkoxy silane base, More preferably there is the compound of trialkoxy silane base.
The alkoxysilane compound containing trialkylsilyl group in molecular structure that can be used in the present invention is preferably and makes base material, such as silicon such as silicon, silicon oxide, silicon nitride The compound that the adhesion of the metals such as compound, gold, copper, molybdenum, titanium, aluminum and dielectric film is improved.Specifically, known silane idol Mixture etc. is also effective.Preferably there is the silane coupling agent of ethylene unsaturated bond.
Silane coupling agent can for example be enumerated：Gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl dialkoxy silicane, γ-methacryl Epoxide propyl trialkoxy silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4- epoxycyclohexyl) ethyltrialkoxysilanes, vinyl tri-alkoxy silicon Alkane.In these compounds, more preferably γ-methacryloxypropyl trialkoxy silane, γ-acryloxypropyl three Alkoxy silane, vinyl trialkyl oxysilane, γ-glycidyloxypropyl silane.These compounds can be single Solely use a kind of or be applied in combination two or more.
Commercially available product can illustrate KBM-403 or the KBM-5103 that SHIN-ETSU HANTOTAI's chemical industry (stock) is manufactured.
Relative to the total solid content of photosensitive composite, the alkoxy silane chemical combination in the photosensitive composite of the present invention The content of thing is preferably 0.1 mass %～30 mass %, more preferably 2 mass %～27 mass %, and then preferably 3 mass % ～24 mass %.Alkoxysilane compound containing trialkylsilyl group in molecular structure only using one kind can also can contain two or more.Containing two or more situations When, preferably total amount becomes the scope.
(other compositions)
The photosensitive composite of the present invention can contain other compositions in addition to the composition, also.Other compositions can be illustrated：Tool There are the compound of epoxy radicals, the compound with oxetanylmethoxy.
<Compound with epoxy radicals and the compound with oxetanylmethoxy>
The photosensitive composite of the present invention also can contain selected from the compound with epoxy radicals and have oxetanylmethoxy The group that constituted of compound at least one.If the form, then the hardness of the cured film of gained is more excellent.
(there is the compound of epoxy radicals)
The photosensitive composite of the present invention can also contain the compound with epoxy radicals.Compound with epoxy radicals can be Only there are 1 epoxy radicals, it is however preferred to have more than 2 in molecule.
Can enumerate in the concrete example of compound of the intramolecular with the epoxy radicals of more than 2：It is bisphenol A type epoxy resin, double Phenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc..
These compounds can be obtained as commercially available product.For example, bisphenol A type epoxy resin be JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (are Japanese epoxy above Resin (Japan Epoxy Resin) (stock) manufacture), Chinese mugwort than clone (EPICLON) 860, Chinese mugwort than clone (EPICLON) 1050, Chinese mugwort is than clone (EPICLON) 1051, Chinese mugwort than clone (EPICLON) 1055 (manufacturing for Di Aisheng (DIC) (stock) above) etc.；Bis-phenol F types epoxy resin (is Japanese epoxy resin for JER806, JER807, JER4004, JER4005, JER4007, JER4010 above (Japan Epoxy Resin) (stock) is manufactured), Chinese mugwort than clone (EPICLON) 830, Chinese mugwort than clone (EPICLON) 835 (is above Di Aisheng (DIC) (stock) is manufactured), LCE-21, RE-602S (manufacturing for Japanese chemical medicine (stock) above) etc.；Phenol novolak type Epoxy resin (is Japanese epoxy resin (Japan Epoxy for JER152, JER154, JER157S70, JER157S65 above Resin) (stock) manufacture), Chinese mugwort is than clone (EPICLON) N-740, Chinese mugwort than clone (EPICLON) N-740, Chinese mugwort than clone (EPICLON) N-770, Chinese mugwort are than clone (EPICLON) N-775 (manufacturing for Di Aisheng (DIC) (stock) above) etc.；Cresol novolac is clear Paint shaped epoxy resin is Chinese mugwort than cloning (EPICLON) N-660, Chinese mugwort than clone (EPICLON) N-665, Chinese mugwort ratio clone (EPICLON) N-670, Chinese mugwort are than clone (EPICLON) N-673, Chinese mugwort than clone (EPICLON) N-680, Chinese mugwort than clone (EPICLON) N-690, Chinese mugwort Than cloning (EPICLON) N-695 (manufacturing for Di Aisheng (DIC) (stock) above), EOCN-1020 (is Japanese chemical medicine (stock) above Manufacture) etc.；Aliphatic epoxy resin is Ai Dike resins (ADEKA RESIN) EP-4080S, Ai Dike resin (ADEKA RESIN) EP-4085S, Ai Dike resin (ADEKA RESIN) EP-4088S (manufacturing for Ai Dike (ADEKA) (stock) above), (Celloxide) 2021P, Sai Luo West Germany of Sai Luo West Germany (Celloxide) 2081, Sai Luo West Germany (Celloxide) 2083, match sieve West Germany (Celloxide) 2085, EHPE3150, Ai Boli obtains (EPOLEAD) PB 3600, Ai Boli and obtains (EPOLEAD) PB 4700 (manufacturing for Daicel (Daicel) chemical industry (stock) above) etc..Can also enumerate in addition：Ai Dike resins (ADEKA RESIN) EP-4000S, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike resin (ADEKA RESIN) EP-4010S, Ai Dike resin (ADEKA RESIN) EP-4011S (is manufactured for Ai Dike (ADEKA) (stock)) above, NC- 2000th, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufacturing for Ai Dike (ADEKA) (stock) above) Deng.
In addition, also preferably using Japan Patent examined patent publication 58-49860 publication, Japan Patent examined patent publication 56- Described in No. 17654 publications, Japan Patent examined patent publication 62-39417 publication, Japan Patent examined patent publication 62-39418 publications Carbamate compounds class with skeletal oxirane, these contents are incorporated to into present specification.
When the photosensitive composite of the present invention contains the situation of the compound with epoxy radicals, preferably with compositionss The scope of 0.1 mass %～20 mass % of total solid content and contain, more preferably with the model of 0.5 mass %～10 mass % Enclose and contain, and then preferably contained with the scope of 1 mass %～5 mass %.
The photosensitive composite of the present invention can only contain a kind of compound with epoxy radicals, can also contain two or more. When containing two or more situations, preferably total amount becomes the scope.
(there is the compound of oxetanylmethoxy)
The photosensitive composite of the present invention can also contain the compound with oxetanylmethoxy.Change with oxetanylmethoxy Compound can only have 1 oxetanylmethoxy in the molecule, it is however preferred to have more than 2.
The concrete example of the compound with oxetanylmethoxy can be used：Sub- dragon oxetanes (Aron Oxetane) OXT- 121st, sub- dragon oxetanes (Aron Oxetane) OXT-221, sub- dragon oxetanes (Aron Oxetane) OX-SQ, Asia Imperial oxetanes (Aron Oxetane) PNOX (being East Asia synthesis (stock) manufacture above).
In addition, the compound containing oxetanylmethoxy is preferably used alone or is mixed with the compound containing epoxy radicals making With.
When the photosensitive composite of the present invention contains the situation of the compound with oxetanylmethoxy, preferably with combination The scope of 0.1 mass %～20 mass % of the total solid content of thing and contain, more preferably with 0.5 mass %～10 mass % Scope and contain, and then be preferably contained with the scope of 1 mass %～5 mass %.
The present invention photosensitive composite only can contain a kind of compound with oxetanylmethoxy, also can contain two kinds with On.When containing two or more situations, preferably total amount becomes the scope.
In the photosensitive composite of the present invention, also can be in the range of the purport without departing from the present invention containing beyond described Other compounds (such as compound containing alkoxy methyl etc.).Compound containing alkoxy methyl can enumerate Japanese Patent Laid-Open Person described in the 0192～paragraph of paragraph 0194 of 2011-221494 publications.
<Surfactant>
The photosensitive composite of the present invention also can be containing the surfactant as other compositions.
Surfactant can use any one of anion system, cation system, nonionic system or both sexes, and preferred surface is lived Property agent be nonionic surfactants.Surfactant is preferably nonionic surfactants, more preferably fluorine system surface Activating agent.
The surfactant that can be used in the present invention can for example be enumerated：Mei Jiafa (Megafac) as commercially available product F142D, Mei Jiafa (Megafac) F172, Mei Jiafa (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F177, Mei Jiafa (Megafac) F183, Mei Jiafa (Megafac) F479, Mei Jiafa (Megafac) F482, U.S. Good method (Megafac) F554, Mei Jiafa (Megafac) F780, Mei Jiafa (Megafac) F781, Mei Jiafa (Megafac) F781-F, Mei Jiafa (Megafac) R30, Mei Jiafa (Megafac) R08, Mei Jiafa (Megafac) F-472SF, Mei Jiafa (Megafac) BL20, Mei Jiafa (Megafac) R-61, Mei Jiafa (Megafac) R-90 (Di Aisheng (DIC) (stock) manufactures), not Rad (Fluorad) FC-135, Fu Lade (Fluorad) FC-170C, Fu Lade (Fluorad) FC-430, Fu Lade (Fluorad) FC-431, Nuo Beike (Novec) FC-4430 (Sumitomo 3M (stock) manufactures), rising sun Jiade (Asahi Guard) AG7105, rising sun Jiade (Asahi Guard) 7000, rising sun Jiade (Asahi Guard) 950, rising sun Jiade (Asahi Guard) 7600th, Sha Fulong (Surflon) S-112, Sha Fulong (Surflon) S-113, Sha Fulong (Surflon) S-131, Sha Fulong (Surflon) S-141, Sha Fulong (Surflon) S-145, Sha Fulong (Surflon) S-382, Sha Fulong (Surflon) SC- 101st, Sha Fulong (Surflon) SC-102, Sha Fulong (Surflon) SC-103, Sha Fulong (Surflon) SC-104, Sha Fulong (Surflon) SC-105, Sha Fulong (Surflon) SC-106 (Asahi Glass (stock) manufacture), Ai Futuo (Eftop) EF351, Ai Fu Open up (Eftop) 352, Ai Futuo (Eftop) 801, Ai Futuo (Eftop) 802 (Mitsubishi Materials electronics chemical conversion (stock) manufacture), Fu Ji Spy (Ftergent) 250 (Ni Aosi (Neos) (stock) manufactures).In addition, in addition to described, can also enumerate：KP (SHIN-ETSU HANTOTAI's chemistry Industrial (stock) manufacture), Bao Lifuluo (Ployflow) (common prosperity society chemistry (stock) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials electricity Son chemical conversion (stock) manufacture), Mei Jiafa (Megafac) (Di Aisheng (DIC) (stock) manufactures), Fu Lade (Fluorad) (Sumitomo 3M (stock) is manufactured), rising sun Jiade (Asahi Guard), Sha Fulong (Surflon) (Asahi Glass (stock) manufacture), precious manage Floex (PolyFox) each series such as (manufacture of Europe Nova (OMNOVA) company).
In addition, surfactant can enumerate following copolymer as preference, the copolymer contains represented by following formula W Component units A and Component units B, and the polystyrene determined by gel permeation chromatography using tetrahydrofuran as solvent The weight average molecular weight (Mw) of conversion is more than 1,000 and less than 10,000.
[changing 11]
In formula W, RW1 and RW3 separately represents hydrogen atom or methyl, and RW2 represents the straight of carbon number more than 1 and less than 4 Chain alkylidene, RW4 represent the alkyl of hydrogen atom or carbon number more than 1 and less than 4, and LW represents the alkylene of carbon number more than 3 and less than 6 Base, p and q are the quality percentage for representing polymerization ratio, and p represents more than 10 mass % and the numerical value below 80 mass %, and q represents 20 Numerical value more than quality % and below 90 mass %, r represent more than 1 and less than 18 integer, and s represents more than 1 and less than 10 Integer.
The LW is preferably the branched alkylene groups represented by following formula W-2.RW5 in formula W-2 represents carbon number more than 1 and 4 Following alkyl, with regard to the compatibility and for the aspect of the wetting quality in applied face, the preferably alkane of carbon number more than 1 and less than 3 Base, the more preferably alkyl of carbon number 2 or 3.
P in formula W is with q's and (p+q) is preferably p+q=100, i.e. 100 mass %.
The weight average molecular weight (Mw) of the copolymer more preferably more than 1,500 and less than 5,000.
[changing 12]
With regard to the content of the surfactant in the photosensitive composite of the present invention, in the situation of allotment surfactant When, relative to the total solid content of compositionss, the content of the surfactant is preferably 0.001 mass %～5.0 mass %, More preferably 0.01 mass %～2.0 mass %.
Surfactant only containing one kind can also can contain two or more.When containing two or more situations, preferably Its total amount becomes the scope.
<Antioxidant>
The photosensitive composite of the present invention can contain antioxidant in addition to the composition, also.Furthermore, antioxidant be except Compound beyond the composition K.Antioxidant can contain known antioxidant.By adding antioxidant, having to prevent The coloring of cured film can reduce that thickness caused by decomposing is thinning, the excellent advantage of heat resistant transparent in addition.
This kind of antioxidant can for example be enumerated：It is phosphorous antioxidant, amide-type, hydrazides class, hindered phenol series antioxidant, anti- Bad hematic acid class, zinc sulfate, saccharide, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc..It is in these, just hard For changing the thinning viewpoint of the coloring of film, thickness, especially preferably hindered phenol series antioxidant, phosphorous antioxidant, most preferably For hindered phenol series antioxidant.These antioxidants can be used alone one kind, can also mix two or more.
Preferred commercially available product can be enumerated：Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripples (Adekastab) AO-80 (manufacturing for Ai Dike (ADEKA) (stock) above), gorgeous Northey (Irganox) 1098 (is Bath above Husband (BASF) company manufactures).
There is no particular restriction for the content of antioxidant, relative to the total solid content of photosensitive composite, preferably 0.1 matter Amount %～10 mass %, more preferably 0.2 mass %～5 mass %, and then preferably 0.5 mass %～4 mass %.
<Binder polymer>
For improving the viewpoint such as analyticity and epithelium characteristic, the photosensitive composite of the present invention also can be poly- containing binding agent Compound.
There is no particular restriction for binder polymer, can use known person, it is preferable to use linear organic polymer.This kind of line Property organic polymer can arbitrarily use known person.Preferably select in water or alkalescent water as solubility or bloating tendency linear Organic polymer, so that water development or alkalescent water development can be carried out.Linear organic polymer is formed according to serving not only as epithelium Agent and select as the purposes of water or alkalescent water or organic solvent developing agent use.If for example being had using water dissolvable Machine polymer, then can carry out water development.This kind of linear organic polymer can be enumerated：The radical polymerization with carboxylic acid group on side chain Zoarium, such as Japanese Patent Laid-Open No. Sho 59-44615 publication, Japan Patent examined patent publication 54-34327 publication, Japan Patent are special Public clear 58-12577 publications, Japan Patent examined patent publication 54-25957 publication, Japanese Patent Laid-Open No. Sho 54-92723 publication Publication, Japanese Patent Laid-Open No. Sho 59-53836 publication, person described in Japanese Patent Laid-Open No. Sho 59-71048 publication, i.e. make Monomer with carboxyl carries out the resin of homopolymerization or combined polymerization, makes the monomer with anhydride carry out homopolymerization or combined polymerization And make anhydride unit hydrolysis or half-esterification or semi-amidation resin, make epoxy resin using unsaturated monocarboxylic and anhydride Modified epoxy acrylate etc..Monomer with carboxyl can be enumerated：Acrylic acid, methacrylic acid, itaconic acid, butylene Acid, maleic acid, fumaric acid, 4- carboxyl styrenes etc., the monomer with anhydride can enumerate maleic anhydride etc..
Additionally, there are the similarly acid cellulose derivant with carboxylic acid group on side chain.In addition, with hydroxyl On the polymer of base, compound of addition cyclic acid anhydride etc. is useful.
There is no particular restriction for the content of the binder polymer in the photosensitive composite of the present invention, relative to photonasty group The total solid content of compound, preferably 0 mass %～40 mass %, more preferably 0 mass %～30 mass %, and then be preferably 0 mass %～20 mass %, especially preferably 0 mass %～10 mass %, most preferably 0 mass %～5 mass %.
Relative to the total solid content of photosensitive composite, the weight average molecular weight in the photosensitive composite of the present invention The content of the component of polymer more than 10,000 is preferably 0 mass %～40 mass %, more preferably 0 mass %～30 matter Amount %, and then preferably 0 mass %～20 mass %, especially preferably 0 mass %～10 mass %, most preferably 0 mass % ～5 mass %.
If the content of component of polymer is in the scope, developability and hardening are excellent.
(other compositions)
In the photosensitive composite of the present invention, in addition to composition mentioned above, optionally can also add plasticiser, heat The other compositions such as acid producing agent, acid proliferation generator.With regard to these compositions, for example can be public using Japanese Patent Laid-Open 2009-98616 Report, person described in Japanese Patent Laid-Open 2009-244801 publication and person known in other.In addition, also can be by《Polymeric additive New expansion (daily magazine industry newspaper office (stock))》Described in various UV absorbent or matal deactivator etc. add to the present invention Photosensitive composite in.
<The composition of photosensitive composite>
The photosensitive composite of the present invention is preferably and contains 3 matter relative to the total organic solid composition of photosensitive composite Composition A, the composition B containing 20 mass %～85 mass % of amount %～49.5 mass %, containing 0.5 mass %～30 mass % Composition C, the composition N containing 0.1 mass %～20 mass %, and the composition K containing 0.01 mass %～0.5 mass %.
<Cured film, hardening thing and its manufacture method>
The hardening thing of the present invention is the hardening thing of the photosensitive composite hardening for making the present invention.The hardening thing is preferred For cured film.In addition, the cured film of the present invention preferably utilizes the cured film obtained by the manufacture method of the cured film of the present invention.
As long as the manufacture method of the cured film of the present invention manufactures cured film to make the photosensitive composite hardening of the present invention Method, then there is no particular restriction, preferably sequentially comprises the following steps 1～step 5.
Step 1：Application step, the photosensitive composite of the present invention is coated on substrate
Step 2：Solvent removal step, removes solvent from the photosensitive composite being coated with
Step 3：Step of exposure, is carried out at least a portion for eliminating the photosensitive composite of solvent using actinic ray Exposure
Step 4：Development step, is developed to exposed photosensitive composite using aqueous developer solution
Step 5：Heat treatment step, carries out heat treatment to developed photosensitive composite
In addition, the manufacture method of the cured film of the present invention more preferably includes after below step 4, before step 5 Below step 4 '.
Step 4 '：Further to developed photosensitive composite irradiation actinic ray the step of
In the application step, preferably the photosensitive composite of the present invention is coated on substrate and is made containing molten The moistening film of agent.Before photosensitive composite is coated on substrate, the substrates such as alkali cleaning or plasma clean can be carried out Cleaning.Further, substrate surface can be processed using hexamethyldisiloxane etc. after base-plate cleaning.By carry out this at Reason, has the tendency of photosensitive composite and the adhesion of substrate is improved.
The substrate can enumerate inorganic substrate, resin, resin composite materials etc..
Inorganic substrate can for example be enumerated：Glass, quartz, silicon, silicon nitride and on this kind of substrate evaporation have molybdenum, titanium, aluminum, copper Etc. composite base plate.
With regard to resin, the substrate comprising following resin can be enumerated：Polybutylene terephthalate, poly terephthalic acid second two Ester, PEN, poly- naphthalenedicarboxylic acid fourth diester, polystyrene, Merlon, polysulfones, polyether sulfone, polyarylate, alkene It is propyl group diglycol carbonates, polyamide, polyimides, polyamidoimide, Polyetherimide, polybenzoxazole, polyphenylene sulfide, poly- The fluororesin such as cycloolefins, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicon Ketone resin, ionomeric resins, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic ether, maleimide The synthetic resin such as amine-ene hydrocarbon copolymer, cellulose, episulfide resin.
These substrates are seldom directly used with the form, such as TFT are formed with depending on the form of final products generally first The multilayer laminate constructions of part.
In addition, on for unit during the situation of touch screen of structure etc., also can be by the photosensitive composite application of the present invention In liquid crystal display (liquid-crystal display, the LCD) unit or organic light emission that are temporarily completed in the form of panel On diode (Organic light emitting diode, OLED) unit.
The photosensitive composite of the present invention is good to the contiguity of the metal film or metal-oxide of the masking by sputter, therefore Substrate is preferably the metal film containing the masking by sputter.Metal be preferably titanium, copper, aluminum, indium, stannum, manganese, nickel, cobalt, molybdenum, tungsten, The oxide or alloy of chromium, silver, neodymium and these metals, and then the preferably alloy of molybdenum, titanium, aluminum, copper and these metals.Furthermore, Metal or metal-oxide can be used alone one kind, also can simultaneously with various.
The coating process of substrate is not particularly limited, for example, can be used：Ink-jet method, slot coated method, nebulization, roll-type The method such as rubbing method, method of spin coating, cast coating method, slit and circumgyration, print process.
In the solvent removal step, preferably by decompression (vacuum) and/or heating etc. from the film being coated with It is middle to remove solvent and dry coating is formed on substrate.The heating condition of solvent removal step is preferably at 70 DEG C～130 DEG C Heating 30 seconds～300 seconds or so.In addition, in the solvent removal step, need not be by the solvent in photosensitive composite Remove completely, as long as at least a portion is removed.
In the step of exposure, preferably to the film of gained with more than pattern-like illumination wavelength 300nm that specifies and The actinic ray of below 450nm.In the step, polymerism list amount body is polymerized by the effect of Photoepolymerizationinitiater initiater firmly Change.
Exposure light source can be using low pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, LED light source, standard point Sub- laser generator etc., it is preferable to there is wavelength using i rays (365nm), h rays (405nm), g rays (436nm) etc. For more than 300nm and the actinic ray of the wavelength of below 450nm.In addition, also can optionally pass through long wavelength cutoff wave filter, short Wavelength cut-off wave filter, the light splitting wave filter of band filter and adjust irradiation light.
Exposure device can using mirror surface projection aligner, stepper, scanning device, close induction type, contact, microlens array, The exposure machine of the various modes such as lens scan device, laser explosure.
In addition, the light exposure in the step of exposure is also not particularly limited, preferably 1mJ/cm2～3,000mJ/cm2, more Preferably 1mJ/cm2～500mJ/cm2.
For promoting the viewpoint of hardening, the exposure in the step of exposure is preferably carried out in the state of oxygen stop. Stop that the method for oxygen can be illustrated：It is exposed in a nitrogen environment, or oxygen barrier film is set.
As long as in addition, at least a portion of the curable adhensive compositions to eliminating solvent carries out the exposure in the step of exposure Light, for example, can be blanket exposure, alternatively pattern exposure.In the present invention, step of exposure is preferably pattern exposure, more preferably It is the step of being exposed via photomask.
In addition, post-heating can be exposed after the step of exposure processes (Post Exposure Bake) (below Referred to as " PEB ").Temperature when carrying out PEB be preferably more than 30 DEG C and less than 130 DEG C, more preferably more than 40 DEG C and 120 DEG C with Under, especially preferably more than 50 DEG C and less than 110 DEG C.
The method of heating is not particularly limited, and can use known method.Heating plate, baking oven, infrared ray can for example be enumerated Heater etc..
In addition, with regard to heat time heating time, preferably 1 minute～30 minutes or so in the case of heating plate, in addition In the case of be preferably 20 minutes～120 minutes or so.Within the range, damage can not be caused to substrate, device and is heated.
In development step, the unhardened portion using aqueous developer solution to exposure for the photosensitive composite of pattern-like is carried out Development is simultaneously removed, and forms negative image.Developer solution used in development step is preferably the aqueous developer solution of alkalescence.
Developer solution used in development step is preferably the aqueous solution of alkali compoundss.Alkali compoundss can for example be used： The alkali metal hydroxides such as Lithium hydrate, sodium hydroxide, potassium hydroxide；The alkali metal carbonic acid such as sodium carbonate, potassium carbonate, cesium carbonate Salt；The alkali metal hydrogencarbonate class such as sodium bicarbonate, potassium bicarbonate；Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl The tetra-alkyl ammonium hydroxide class such as ammonium hydroxide, TBAH, diethyl-dimethyl ammonium hydroxide；(the hydroxyl alkane such as choline Base) trialkylammonium hydroxides class；The silicates such as sodium silicate, sodium metasilicate；The alkylamines such as ethamine, propylamine, diethylamine, triethylamine Class；The alcaminess such as dimethylethanolamine, triethanolamine；1,8- diazabicyclo [5.4.0] -7- hendecenes, 1,5- diazas are double The ester ring type amines such as ring [4.3.0] -5- nonenes.
Sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl hydrogen are preferably in these Amine-oxides, TBAH, choline (2- hydroxyethyl trimethylammonium hydroxides).
In addition, it is organic to be added with the water solublity such as the methanol or ethanol of appropriate amount in can be used on the aqueous solution of the bases The aqueous solution of solvent or surfactant is used as developer solution.
Preferred developer solution can enumerate the aqueous solution of 0.4 mass %～2.5 mass % of Tetramethylammonium hydroxide.
The pH of developer solution is preferably 10.0～14.0.
Developing time is preferably 30 seconds～500 seconds, in addition, the method for development can (puddle formula be developed for covering liquid method Method), spray process, the anyone of infusion process etc..
After development step, rinsing step can be also carried out.In rinsing step, the substrate after development is entered using pure water etc. Row cleaning, accompanying developer solution is removed, so as to remove development residue.ELUTION METHOD can use known method.For example may be used Enumerate spray drip washing or dipping drip washing etc..
With regard to pattern exposure and development, known method or known developer solution can be used.Day is preferably used for example Pattern exposure method described in this patent JP 2011-186398 publication, Japanese Patent Laid-Open 2013-83937 publication And developing method.
In addition, for improving the viewpoint of film hardness, preferably after development step, before heat treatment step, including entering one Walk to (post-exposure) the step of developed photosensitive composite irradiation actinic ray.
In the situation, the energy of 50mJ/cm2～3,000mJ/cm2 or so is preferably carried out using finsen lamp or LED etc. Amount exposure.In addition, with regard to post-exposure, preferably carrying out blanket exposure.
By carrying out post-exposure, can further promote the sclerous reaction of film, so as to film hardness is improved.
The manufacture method of the cured film of the present invention is preferably to be included to developed photonasty group after the development step The step of compound carries out heat treatment (is toasted) afterwards.By carrying out heat treatment to the photosensitive composite of the present invention after development, can Obtain the more excellent cured film of intensity.
The temperature of heat treatment is preferably less than 180 DEG C, more preferably less than 150 DEG C, and then preferably less than 130 DEG C.Under Limit value is preferably more than 80 DEG C, more preferably more than 90 DEG C.The method of heating is not particularly limited, and can use known method. Heating plate, baking oven, infrared heater etc. can for example be enumerated.
In addition, with regard to heat time heating time, preferably 1 minute～30 minutes or so in the case of heating plate, in addition In the case of be preferably 20 minutes～120 minutes or so.Within the range, damage can not be caused to substrate, device and is hardened.
In addition, the hardening of the utilization light and/or heat in the manufacture method of the cured film of the present invention can be carried out continuously, Can carry out successively.
In addition, when heat treatment is carried out, by carrying out in a nitrogen environment, also can further improve the transparency.
For the viewpoint of the shape after adjustment heating, also can be before heat treatment step (toasting afterwards), than relatively low At a temperature of toasted after, carry out heat treatment step (add in the middle of baking procedure).Can for example illustrate to enter at 90 DEG C first The heating of row 30 minutes (middle baking), and then method of heating in 30 minutes (toasting afterwards) etc. is carried out at 120 DEG C.In addition, also may be used Middle baking, rear baking were divided into into for 3 the multistages more than stage and are heated.By designing baking in the middle of this kind of, rear baking, The cone angle of adjustable pattern.These heating can be using the known heating means such as heating plate, baking oven, infrared heater.
The cured film of the present invention is the cured film for obtaining the photosensitive composite hardening of the present invention.
The cured film of the present invention is preferably used as outer film (protecting film) or interlayer dielectric.In addition, the present invention's is hard Change film and be preferably the cured film obtained using the manufacture method of the cured film of the present invention.
Photosensitive composite of the invention, even if harden at low temperature Film.Can for example obtain according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) K5600：1999 institutes Cured film of the pencil hardness of the heavy burden 750g of measure for more than 2H.The guarantor for making the photosensitive composite of the present invention harden and be formed Cuticula due to cured film physical properties excellent, therefore in touch screen, touch panel display device, organic EL display, liquid crystal indicator Deng purposes in it is useful.
The photosensitive composite of the present invention is pretended as MEMS (Micro due to hardening and cured film excellent Electro Mechanical Systems, MEMS) device structural elements, will make the present invention photosensitive composite hardening and Into hardening thing or Resist patterns as dividing wall, or enter as a part of group of Mechanical Driven part and use.It is this kind of MEMS devices can for example be enumerated：Surface acoustic wave (Surface Acoustic Wave, SAW) wave filter, bulk acoustic wave (Bulk Acoustic Wave, BAW) wave filter, gyrosensor (gyro sensor), display is with micro- shutter (micro- Shutter), the part such as imageing sensor, Electronic Paper, ink gun, biochip, sealant.More specifically example is to be illustrated in Japanese Patent Laid 2007-522531 publication, Japanese Patent Laid-Open 2008-250200 publication, Japanese Patent Laid-Open 2009- In No. 263544 publications etc..
The photosensitive composite of the present invention is excellent due to flatness or the transparency, therefore for example can also be used for being formed：It is Japanese special Bunding layer (16) and planarization film (57), Japanese Patent Laid-Open described in Fig. 2 of sharp JP 2011-107476 publication Dividing wall (12) and planarization film (102), Japanese Patent Laid-Open 2010- described in Fig. 4 (a) of 2010-9793 publications Bunding floor (221) and the 3rd interlayer dielectric (216b), Japanese Patent Laid-Open 2009- described in Figure 10 of No. 27591 publications The 2nd interlayer dielectric (125) and the 3rd interlayer dielectric (126), Japan Patent described in Fig. 4 (a) of No. 128577 publications is special Open planarization film (12) and pixel separation dielectric film (14) described in Fig. 3 of 2010-182638 publications etc..In addition, Can be preferably also used for：The liquid crystal layer in liquid crystal indicator is held in certain thickness distance piece, liquid crystal display dress The colored filter put or protective films of color filters, facsimile machine (facsimile), electronic reprographic machine, solid-state imager etc. The brilliant imaging optical system or the joints of optical fibre for carrying colored filter (on-chip color filter) lenticule.
<Organic EL display>
The organic EL display of the present invention is characterized by the cured film of the present invention.
The organic EL display of the present invention is except flat with what is formed using the photosensitive composite of the present invention Beyond smoothization film or interlayer dielectric, there is no particular restriction, can enumerate and be shown using known various organic EL of various structures Device or liquid crystal indicator.
Thin film transistor (TFT) that for example, organic EL display of the invention has (Thin-Film Transistor, TFT concrete example) can be enumerated：Non-crystalline silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..The cured film of the present invention Due to excellent electrical characteristic, therefore can combine with these TFT and be preferably used.
Fig. 1 is the composition concept map of of organic EL display, and represents that organic EL of bottom emission type shows dress The constructed profile of the substrate in putting, with planarization film 4.
The TFT 1 of bottom gate type is formed on glass substrate 6, is formed comprising Si3N4 with covering the state of the TFT 1 Dielectric film 3.Formed in dielectric film 3 after omitting the contact hole (contact hole) of diagram herein, formed on the insulating film 3 The distribution 2 (1.0 μm of height) of TFT 1 is connected to via the contact hole.Distribution 2 be to will connection between TFT 1, or will be follow-up The distribution that the organic EL element formed in step is connected with TFT 1.
Further, in order that because forming the concavo-convex planarization caused by distribution 2, to fill concavo-convex state caused by distribution 2 Planarization film 4 is formed on the insulating film 3.
The organic EL element of bottom emission type is formed on planarization film 4.That is, connect via contact hole 7 on planarization film 4 It is connected to distribution 2 and forms the first electrode 5 comprising ITO.In addition, anode of the first electrode 5 equivalent to organic EL element.
The dielectric film 8 of the shape at the edge for covering first electrode 5 is formed, by arranging the dielectric film 8, can prevent first electric Pole 5 and hereafter the step of in short circuit between the second electrode that formed.
Further, in FIG although not shown, but be situated between every required pattern mask come be sequentially deposited with arrange hole transmission layer, have Machine luminescent layer, electron transfer layer, form the second electrode comprising Al, then in the entire surface of surface using sealing glass Glass plate and ultraviolet ray hardening type epoxy resin are fitted, and are thus sealed, and obtain and each organic EL element is connected to drive Move the organic EL display of the active array type of the TFT 1 of each organic EL element.
<Liquid crystal indicator>
The liquid crystal indicator of the present invention is characterized by the cured film of the present invention.
The liquid crystal indicator of the present invention is except with the protection formed using the photosensitive composite of the present invention Beyond film, planarization film or interlayer dielectric, there is no particular restriction, can enumerate the known liquid crystal display dress using various structures Put.
In addition, the liquid crystal drive mode that the liquid crystal indicator of the present invention can be taken can be enumerated：Twisted nematic (Twisted Nematic, TN) mode, vertical orientated (Vertical Alignment, VA) mode, coplanar switching (In-Plane- Switching, IPS) mode, fringing field switching (Fringe Field Switching, FFS) mode, optical compensation curved (Optically Compensated Bend, OCB) mode etc..
Constitute with regard to panel, in the liquid crystal of colorful optical filter array (Color Filter on Array, COA) mode The cured film of the present invention can be also used in showing device, for example, can be used as the organic of Japanese Patent Laid-Open 2005-284291 publication Dielectric film (115), or Japanese Patent Laid-Open 2005-346054 publication organic insulating film (212).In addition, the liquid of the present invention The specific aligned of the liquid crystal orientation film that crystal device can be taken enumerates friction orientation method, optical alignment method etc..In addition, It is possible with described in Japanese Patent Laid-Open 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication Polymer stabilizing is orientated (Polymer Sustained Alignment, PSA) technology to carry out polymer orientation support.
In addition, the cured film of the photosensitive composite and the present invention of the present invention is not limited to the purposes, can be used for various Purposes.For example, in addition to planarization film or interlayer dielectric, it also may be preferable for ground is used for protecting film or to by liquid crystal display Liquid crystal layer in device is held in certain thickness distance piece or is arranged in solid-state imager micro- on colored filter Lens etc..
Fig. 2 is the concept profile of of the liquid crystal indicator 10 for representing active matrix mode.The color liquid crystal shows Showing device 10 is the liquid crystal panel with back light unit 12 on the back side, and in liquid crystal panel, is configured with and is pasted with polarisation The element of the corresponding TFT 16 of all pixels that configure between 2 sheet glass substrates 14 of film, glass substrate 15.For being formed at Each element on glass substrate, carries out forming the transparent of pixel electrode by the contact hole 18 being formed in cured film 17 The distribution of electrode 19.On ito transparent electrode 19, the layer for being provided with liquid crystal 20 and the red-green-blue for being configured with black matrix" (Red Green Blue, RGB) colored filter 22.
The light source of backlight is not particularly limited, and can use known light source.Can for example enumerate：White LED, blueness are red The multi-colored led of color green etc., fluorescent lamp (cold-cathode tube), organic EL etc..
In addition, liquid crystal indicator may be set to three-dimensional (Three dimensions, 3D) (stereopsis) type, can also set For touch screen type.Further, flexible type is also may be set to, is can be used as described in Japanese Patent Laid-Open 2011-145686 publication 2nd interlayer dielectric (48), or Japanese Patent Laid-Open 2009-258758 publication described in interlayer dielectric (520).
<Touch screen and touch panel display device>
The touch screen of the present invention is all or part of combination of hardening comprising the present invention of insulating barrier and/or protective layer The touch screen of the hardening thing of thing.In addition, the touch screen of the present invention preferably at least with transparency carrier, electrode and insulating barrier and/ Or protective layer.
The touch panel display device of touch screen of the touch panel display device of the present invention preferably with the present invention.The present invention Touch screen be alternatively appointing for the known mode such as resistive film mode, electrostatic capacitance mode, ultrasound wave mode, way of electromagnetic induction One.Wherein, preferably electrostatic capacitance mode.
The touch screen of electrostatic capacitance mode can enumerate person or state disclosed in Japanese Patent Laid-Open 2010-28115 publication Border disclose No. 2012/057165 disclosed in person.Other touch screens can be enumerated：(in-cell) type (such as day in so-called unit Fig. 5, Fig. 6, Fig. 7, Fig. 8 of this patent spy's table 2012-517051 publications), so-called unit mo(u)ld top half (such as Japanese Patent Laid-Open Fig. 2 (b) of Figure 14 of 2012-43394 publications, International Publication No. 2012/141148), one chip glass touch-control (One Glass Solution, OGS) type, single-layer capacitive touch (Touch On Lens, TOL) type, other are constituted, and (for example Japan is specially Fig. 6 of sharp JP 2013-164871 publication).
In addition, Fig. 3 represents the composition concept map of of the liquid crystal indicator with touch screen function.
For example, cured film of the invention is adapted to be used for protecting film between each layer in figure 3, in addition, can be also suitably used for by The interlayer dielectric that the detecting electrode of touch screen is spaced apart.Furthermore, the detecting electrode of touch screen be preferably silver, copper, aluminum, titanium, molybdenum, The alloy of these metals.
In Fig. 3,110 represent pixel substrate, and 140 represent liquid crystal layer, and 120 represent opposite substrate, and 130 represent sensor portion. Pixel substrate 110 sequentially has Polarizer 111, transparency carrier 112, common electrode 113, insulating barrier from the downside of Fig. 3 114th, pixel electrode 115, alignment films 116.Opposite substrate 120 sequentially has alignment films 121, colored filter from the downside of Fig. 3 Mating plate 122, transparency carrier 123.Sensor portion 130 has phase retardation film 124, following layer 126, Polarizer 127 respectively.In addition, In Fig. 3,125 are sensor detecting electrode.The present invention cured film can be used for pixel substrate part insulating barrier (114) ( Referred to as interlayer dielectric) or various protecting film (not shown), the various protecting film (not shown) of pixel substrate part, opposite substrate Partial various protecting film (not shown), various protecting film (not shown) of Sensor section etc..
Further, in the liquid crystal indicator of static (static) type of drive, also can be shown by applying the present invention The high pattern of design.As an example, can be used as the polymer network described in Japanese Patent Laid-Open 2001-125086 publication The dielectric film of type liquid crystal and the application present invention.
In addition, Fig. 4 is the composition concept map of another of the liquid crystal indicator with touch screen function.
The liquid crystal indicator is included：Possess thin film transistor (TFT) (TFT) 440 equivalent to thin film transistor display panel Bottom display panel 200, it is relative with bottom display panel 200 to and it is relative with bottom display panel 200 to face on possess multiple coloured silks The top display panel 300 equivalent to colored filter display panel of colo(u)r filter 330, and be formed at bottom display panel 200 with Liquid crystal layer 400 between top display panel 300.Liquid crystal layer 400 contains liquid crystal molecule (not shown).
Bottom display panel 200 is containing the 1st insulated substrate 210, the thin film transistor (TFT) being configured on the 1st insulated substrate 210 (TFT) dielectric film 280 that, is formed on the upper surface of thin film transistor (TFT) (TFT), and the pixel electricity that is configured on dielectric film 280 Pole 290.Thin film transistor (TFT) (TFT) can containing gate electrode 220, cover gate electrode 220 gate insulating film 240, quasiconductor Layer 250, ohmic contact layer 260, ohmic contact layer 262, source electrode 270 and drain electrode 272.
In dielectric film 280, contact hole is formed with the way of the drain electrode 272 of thin film transistor (TFT) (TFT) exposes 282。
Top display panel 300 contains：It is configured on a face of the 2nd insulated substrate 310 and with rectangular and screening that arrange Light component 320；The alignment films 350 being configured on the 2nd insulated substrate 310；The colored filter 330 being configured in alignment films 350； And it is configured on colored filter 330 and corresponding with the pixel electrode 290 of bottom display panel 200, electricity is applied to liquid crystal layer 400 The common electrode 370 of pressure.
In the liquid crystal indicator shown in Fig. 4, on the another side of the 2nd insulated substrate 310 configure sensing electrode 410, Dielectric film 420, drive electrode 430 and protecting film 280.Thus, in the manufacture of the liquid crystal indicator shown in Fig. 4, being formed During the display panel 300 of top, the sensing electrode 410, absolutely of element as touch screen (touch screen) can be formed in the lump Velum 420 and drive electrode 430 etc..Especially can be preferably used as the cured film of the photosensitive composite hardening of the present invention Dielectric film 280 or dielectric film 420.
[embodiment]
It is exemplified below embodiment to be more particularly described the present invention.Material, usage amount shown in below example, Ratio, process content, processing sequence etc. then suitably can be changed without departing from the purport of the present invention.Therefore, the scope of the present invention It is not limited to concrete example shown below.Furthermore, as long as no special instructions, then " part ", " % " are quality criteria.
Each composition used in embodiment and comparative example is as described below.
(composition A)
a-1：The compound of following structures
a-2：The compound of following structures
a-3：The compound of following structures
a′-1：Sieve Ah Nice (Aronix) M-5300 (East Asia synthesis (stock) manufacture), 1 sense
[changing 13]
(composition B)
b-1：Dipentaerythritol acrylate (DPHA, Japanese chemical medicine (stock) manufacture), 6 senses
b-2：Tetramethylol methane tetraacrylate (A-TMMT, Xin Zhong village chemical industry (stock) manufacture), 4 senses
b-3：Trimethylolpropane trimethacrylate (M309, East Asia synthesis (stock) manufacture), 3 senses
b-4：NK oligomerizations (NK OLIGO) U-15HA (Xin Zhong villages chemical industry (stock) manufacture), 15 senses
b-5：UA-306H (common prosperity society chemistry (stock) manufacture), 6 senses
B ' -1: 1,9- nonanediol diacrylate (A-NOD-N, Xin Zhong village chemical industry (stock) manufacture), 2 senses
(composition C)
C-1：Compound 1 (composite, with reference to following), oxime ester compound
C-2：Gorgeous good solid (IRGACURE) OXE-01 (manufacture of BASF (BASF) company), oxime ester compound, following structures
C-3：Gorgeous good solid (IRGACURE) OXE-02 (manufacture of BASF (BASF) company), oxime ester compound, following structures
[changing 14]
(composition K)
K-1：Phenothiazine (Tokyo chemical conversion industry (stock) manufacture)
K-2：Phenoxazine (Tokyo chemical conversion industry (stock) manufacture)
(composition E)
E-1：PMA-ST (Nissan Chemical Industries (stock) manufacture), silicon dioxide granule, mean diameter are 10nm～15nm
E-2：MIBK-ST-L (Nissan Chemical Industries (stock) manufacture), silicon dioxide granule, mean diameter are 40nm～50nm
(composition N)
N-1：Plutarch Nat (Takenate) B870N (Mitsui Chemicals (stock) manufacture) (substrate isocyanates：Isophorone two Isocyanates, sealer：Methyl ethyl ketone (Methyl ethyl ketone, MEK) oxime)
N-2：De Simo (Desmodule) BL3575/1MPA/SN (firmly changes Bayer (Sumitomo-Bayer) (stock) manufacture) (substrate isocyanates：Hexamethylene diisocyanate, sealer：Methyl ethyl ketone oxime)
N-3：De Simo (Desmodule) BL4265SN (firmly changing Bayer (Sumitomo-Bayer) (stock) manufacture) (substrate Isocyanates：Isophorone diisocyanate, sealer：Methyl ethyl ketone oxime)
N-4：Du draws Nat (Duranate) SBN-70D (Mitsui Chemicals (stock) manufacture) (substrate isocyanates：1,6- six is sub- Methyl diisocyanate, sealer：Pyrazole derivatives)
(composition S)
SC-1：KBM-403 (3- glycidoxypropyltrimewasxysilanes, SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture)
SC-2：KBM-5103 (3- acryloxypropyl trimethoxy silanes, SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture)
(components D)
D-1：Propylene glycol methyl ether acetate (Daicel (Daicel) (stock) manufacture)
D-2：Methylethyl diethylene glycol (Daicel (Daicel) (stock) manufacture)
D-3: 1,3 butylene glycol diacetate esters
D-4：Tetrahydrofurfuryl alcohol
(surfactant)
W-1：Mei Jiafa (Megafac) F554 (Di Aisheng (DIC) (stock) manufactures), fluorine system surfactant
(sensitizer)
I-1：DBA (the dibutoxy anthracenes of following structures) (Kawasaki chemical conversion industry (stock) manufacture)
(antioxidant)
J-1：Ai Di Coase tower ripple (Adekastab) AO-60 (hindered phenol series antioxidant, Ai Dike (ADEKA) (stock) systems Make)
[changing 15]
(in formula, Bu represents butyl)
<The synthesis of compound 1 (C-1)>
(synthesis of compound A)
Ethyl carbazole (100.0g, 0.512mol) is dissolved in chlorobenzene 260ml, after being cooled to 0 DEG C, adds aluminum chloride (70.3g、0.527mol).Then, with 40 minutes Deca toluoyl chlorine (81.5g, 0.527mol), be warming up to room temperature (25 DEG C, It is same as below) and stir 3 hours.It is then cooled to after 0 DEG C, add aluminum chloride (75.1g, 0.563mol).With 40 minutes Deca 4- chlorobutanoylchlorides (79.4g, 0.563mol), are warming up to room temperature and stir 3 hours.By 35 mass % aqueous hydrochloric acid solution 156ml with The mixed solution of distilled water 392ml is cooled to 0 DEG C, dropwise reaction solution.After solid to separating out is filtered by suction, using steaming Distilled water and methanol are cleaned, and after being recrystallized using acetonitrile, (yield is 164.4g to the compound A of the following structures of acquisition, is produced 77%) rate is.
[changing 16]
(synthesis of compound B)
The compound A (20.0g, 47.9mmol) of the acquisition is dissolved in tetrahydrofuran (THF) 64ml, adds 4- chlorine Benzenethiol (7.27g, 50.2mmol) and sodium iodide (0.7g, 4.79mmol).Then, add sodium hydroxide in reactant liquor (2.0g, 50.2mmol), flows back 2 hours.Then, after being cooled to 0 DEG C, with 20 minutes Deca SM-28 (11.1g, 57.4mmol, 28% methanol solution of methoxylation sodium, and Wako Pure Chemical Industries (stock) manufacture), it is warming up to room temperature and stirs 2 hours.Then, cool down To after 0 DEG C, with 20 minutes Deca amyl nitrite (6.73g, 57.4mmol), it is warming up to room temperature and stirs 3 hours.Will reaction Liquid is diluted in acetone 120ml, is dropped to and is cooled in 0 DEG C of 0.1N aqueous hydrochloric acid solutions.Solid to separating out is aspirated After filtration, cleaned using distilled water.Then recrystallized using acetonitrile, (yield is to obtain the compound B of following structures 17.0g, yield are for 64%).
[changing 17]
(synthesis of compound 1)
Compound B (18.0g, 32.4mmol) is dissolved in the N-Methyl pyrrolidone (NMP) of 90ml, adds triethylamine (Et3N, 3.94g, 38.9mmol).Then, after being cooled to 0 DEG C, with 20 minutes Deca chloroacetic chlorides (AcCl, 3.05g, After 38.9mmol), it is warming up to room temperature and stirs 2 hours.Reactant liquor is dropped to and is cooled in 0 DEG C of distilled water 150ml, it is right After the solid of precipitation is filtered by suction, cleaned using the isopropanol 200ml for being cooled to 0 DEG C, after being dried, obtained chemical combination (yield is 19.5g to thing 1, and 99%) yield is.
[changing 18]
In addition, the structure of the compound 1 of gained be using nuclear magnetic resonance, NMR (Nuclear Magnetic Resonance, NMR) identifying.
1H-NMR (400MHz, CDCl3)：δ=8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J=8.0Hz), 8.81 (d, 1H, J=8.0Hz), 7.51-7.24 (m, 10H), 7.36 (q, 2H, 7.4Hz), 3.24-3.13 (m, 4H), 2.36 (s, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4Hz).
(1～embodiment of embodiment 100 and 1～comparative example of comparative example 10)
<The preparation of photosensitive composite>
Solution and/or the dispersion of organic solvent is made in each composition allotment stirring as described in table 1 below～table 3 Liquid, is filtered using the politef filter that aperture is 0.3 μm, obtains the photosensitive composite of the present invention.Except Beyond solid component concentration, the unit of each composition of following tables is mass parts.In addition, representing beyond organic solvent that solid constituent is changed The mass parts of calculation.
Furthermore, the composition A used in comparative example 9 has following described in the embodiment 1 of Japanese Patent No. 05201066 Composition.In addition, in comparative example 10, being added with the amount of 0.2 mass % equivalent to total solid content amount relative to the composition A Phenothiazine.
(composition A)
Solution of the addition comprising following copolymers (A-1) is (equivalent to 100 mass parts (solid constituent) of copolymer (A-1) Amount), single-[3- (3- acryloxy -2,2- is double-acryloyloxymethyl-propoxyl group) double-acryloyloxymethyls-of -2,2- Propyl group] 200 mass parts of succinate, 2- methyl isophthalic acids-(trade name is gorgeous good for (4- methyl mercapto phenyl) -2- morpholinopropanes -1- ketone (Gu IRGACURE) 907, Ciba (Ciba Specialty Chemicals) company manufacture) 10 mass parts, novolaks Type epoxy resin (Japanese epoxy resin (Japan Epoxy Resin) (stock) manufacture, trade name Ai Pikaote (Epikote) 152) 30 mass parts, 30 mass parts of γ-glycidoxypropyltrimewasxysilane and the FTX- as surfactant 218 (Ni Aosi (Neos) (stock) manufactures) 0.2 mass parts, and then add molten in the way of solid component concentration becomes 22 weight % After agent diethylene glycol MEE, filtered using the microfilter that aperture is 0.5 μm and prepared.
Furthermore, the copolymer (A-1) obtains as follows.
Add 2 in the flask for possessing cooling tube and blender, double (2,4- methyl pentane nitrile) 5 mass parts of 2 '-azo with 200 mass parts of diethylene glycol MEE.Continuously add 40 mass parts of glycidyl methacrylate, 18 mass of styrene Part, 22 mass parts of 20 mass parts of methacrylic acid and N- N-cyclohexylmaleimides, carry out nitrogen displacement, then start lentamente Stirring.Make solution temperature rise to 70 DEG C, keep the temperature 5 hours, it is molten so as to obtain the polymer comprising copolymer (A-1) Liquid.The solid component concentration of the polymer solution of gained is 33.1 mass %.Gained polymeric number average molecular weight be 7,000 (number average molecular weight is using gel permeation chromatography (Gel Permeation Chromatography, GPC) The polystyrene conversion molecular weight determined by HLC-8020 (eastern Cao's (stock) manufacture)).In addition, molecular weight distribution (Mw/Mn) is 2.
<The evaluation of pattern-forming>
By glass substrate (beneficial lattice (EAGLE) XG, 0.7mm thick (healthy and free from worry (Coming) company manufacture)) in two silicon nitrogen of hexamethyl Expose 30 seconds under alkane (HMDS) steam, after each photosensitive composite of spin application, carry out in 90 DEG C of heating plate 120 seconds Prebake conditions and make solvent volatilize, so as to form the photosensitive composition layer that thickness is 3.0 μm.
Then, the MPA 5500CF (high-pressure mercury-vapor lamp) for being manufactured using Canon's (Canon) (stock), via the mask pair of regulation The photosensitive composition layer of gained is exposed.For light exposure is set as to dissolve when exposed portion is in development fully Light exposure.Then, using alkaline-based developer (2.38% tetramethylammonium hydroxide aqueous solution), at 23 DEG C to exposure after Photosensitive composition layer carries out the development of 60 seconds, and the drip washing of 20 seconds is then carried out using ultra-pure water.Will be by these operations And the most suitable i x ray exposure xs amount (Eopt) during the hole of a diameter of 1mm of parsing is used as sensitivity.
Evaluate using optimal light exposure when parsing each mask footpath to make the permanent film with sectional hole patterns When aperture.In evaluation afterwards, actual sectional hole patterns footpath is specifying with the size of the bottom of resist (basal surface).Aperture (that is, mask rectilinearity (linearity) is high) less with the difference in mask footpath, panel design is easier, so it is preferred that.
Metewand is as follows.
5：The ratio in mask footpath and actual sectional hole patterns footpath is person within ± 10%
4：The ratio in mask footpath and actual sectional hole patterns footpath exceedes ± 10% and for person within ± 20%
3：The ratio in mask footpath and actual sectional hole patterns footpath exceedes ± 20% and for person within ± 30%
2：The ratio in mask footpath and actual sectional hole patterns footpath exceedes ± 30% and for person within ± 40%
1：Mask footpath exceedes ± 40% with the ratio in actual sectional hole patterns footpath
<The salt spraytest (artificial perspiration resistance's fluidity (absorption of perspiration) evaluation test) of cured film>
Each photosensitive composite of the preparation is spun on glass substrate, the preliminary drying of 120 seconds is carried out at 90 DEG C It is roasting, obtain the coated film of 2.0 μm of thickness.Then, the light irradiation of 500mJ/cm2 (conversion of i rays) is carried out using high-pressure mercury-vapor lamp, And then carry out 60 minutes toasting at 120 DEG C using baking oven, cured film is thus made, so as to obtain artificial perspiration resistance's fluidity evaluation use Sample.
Then, with JIS standards (Z 2371) as reference, (testing machine (Suga Test must be congratulated using salt spray tester Instruments) the STP-90V2 that (stock) is manufactured), the sample is placed in test flume, with test flume temperature as 35 DEG C, Spray amount carrys out the saline (pH=6.7) 48 hours that spray concentration is 50g/L for 1.5mL/h.After spraying terminates, saline is wiped away, see The apparent condition of evaluation sample is examined, is evaluated according to following scoring.
5：It is completely unchanged on protecting film surface.
4：In the visible few vestige in protecting film surface, but copper is unchanged.
3：In protecting film surface visible marks, but copper is unchanged.
2：There are vestige, and copper discoloration on protecting film surface.
1：There are vestige, and the rapid discoloration of copper on protecting film surface.
By as indicated in the 1～table of table 3, even if the photosensitive composite of the present invention is hardened at low temperature, it may have high Artificial perspiration resistance's fluidity.
<The making of display device>
In the display device shown in Fig. 4, the photosensitive composite of gained in various embodiments of the present invention is used for into touch-control Detecting electrode protecting film (dielectric film, 420), makes display device respectively.Specifically, protecting film (420) is by with lower section Formula is formed：In slot coated coating various embodiments of the present invention, the photosensitive composite of gained, is carried out at 90 DEG C 120 seconds Prebake conditions, are carried out the light irradiation of 500mJ/cm2 (conversion of i rays) using high-pressure mercury-vapor lamp, and then are entered at 120 DEG C using baking oven Row is toasted for 60 minutes.The other parts of display device be according in Japanese Patent Laid-Open 2013-168125 publication as Figure 19 And the manufacture method recorded is making.The display performance of made display device, touch control detection performance are excellent.
[explanation of symbol]
1：TFT (thin film transistor (TFT))
2：Distribution
3：Dielectric film
4：Planarization film
5：First electrode
6：Glass substrate
7：Contact hole
8：Dielectric film
10：Liquid crystal indicator
12：Back light unit
14、15：Glass substrate
16：TFT
17：Cured film
18：Contact hole
19：Ito transparent electrode
20：Liquid crystal
22：Colored filter
110：Pixel substrate
111：Polarizer
112：Transparency carrier
113：Common electrode
114：Insulating barrier
115：Pixel electrode
116：Alignment films
120：Opposite substrate
121：Alignment films
122：Colored filter
123：Transparency carrier
124：Phase retardation film
125：Sensor detecting electrode
126：Following layer
127：Polarizer
130：Sensor portion
140：Liquid crystal layer
200：Bottom display panel
210：1st insulated substrate
220：Gate electrode
240：Gate insulating film
250：Semiconductor layer
260、262：Ohmic contact layer
270：Source electrode
272：Drain electrode
280：Dielectric film
282：Contact hole
290：Image electrode
300：Top display panel
310：2nd insulated substrate
320：Light obstructing member
330：Colored filter
350：Alignment films
370：Common electrode
400：Liquid crystal layer
410：Sensing electrode
420：Dielectric film
430：Drive electrode
440：TFT

Claims (18)

1. a kind of photosensitive composite, it is characterised in that contain：
As the polymerism list amount with (methyl) acryloyl group of more than 3 and the carboxyl of more than 1 in intramolecular of composition A Body,
There is (methyl) acryloyl group of more than 3 in intramolecular as composition B and there is no the polymerism list amount body of carboxyl,
As the Photoepolymerizationinitiater initiater of composition C,
As the solvent of components D,
As the blocked isocyanate compound of composition N, and
As the polymerization inhibitor of composition K, and
Relative to composition A and the total content of composition B, the content of composition A is 10 mass %～50 mass %.
2. photosensitive composite according to claim 1, wherein relative to the total solid content of photosensitive composite, composition The content of N is 0.1 mass %～20 mass %.
3. photosensitive composite according to claim 1 and 2, wherein relative to composition A and the total content of composition B, composition A Content be 10 mass %～30 mass %.
4. photosensitive composite according to any one of claim 1 to 3, which is also containing the alkoxyl silicone as composition S Hydride compounds.
5. photosensitive composite according to any one of claim 1 to 4, which is also containing the inorganic particulate as composition E.
6. photosensitive composite according to claim 5, wherein relative to the total solid content of photosensitive composite, composition The content of E is 10 mass %～40 mass %.
7. photosensitive composite according to any one of claim 1 to 6, wherein always having relative to photosensitive composite The total content of machine solid constituent, composition A and composition B is 30 mass %～99 mass %.
8. photosensitive composite according to any one of claim 1 to 7, wherein relative to the total solid of photosensitive composite Body composition, the content of component of polymer is below 10 mass %.
9. a kind of manufacture method of cured film, which at least sequentially includes step 1～step 5,
Step 1：Application step, photosensitive composite according to any one of claim 1 to 8 is coated on substrate；
Step 2：Solvent removal step, removes solvent from the photosensitive composite being coated with；
Step 3：Step of exposure, is exposed at least a portion for eliminating the photosensitive composite of solvent using actinic ray Light；
Step 4：Development step, is developed to exposed photosensitive composite using aqueous developer solution；And
Step 5：Heat treatment step, carries out heat treatment to developed photosensitive composite.
10. the manufacture method of cured film according to claim 9, the wherein heat treatment temperature in step 5 are 80 DEG C～180 ℃。
A kind of 11. cured films, which is to form photosensitive composite hardening according to any one of claim 1 to 8.
12. cured films according to claim 11, which is interlayer dielectric or outer film.
13. cured films according to claim 11 or 12, which is the outer film of touch screen.
14. cured films according to any one of claim 11 to 13, which is the outer film of structure touch screen on unit.
A kind of 15. touch screens, which has the cured film according to any one of claim 11 to 14.
A kind of 16. touch panel display devices, which has the cured film according to any one of claim 11 to 14.
A kind of 17. liquid crystal indicators, which has the cured film according to claim 11 or 12.
A kind of 18. organic electroluminescence display device and method of manufacturing same, which has the cured film according to claim 11 or 12.
CN201580038645.7A 2014-07-18 2015-07-07 Photosensitive composition, cured film and method for producing the same, touch panel and display device thereof, liquid crystal display device, and organic EL display device Expired - Fee Related CN106575078B (en)

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